Alignment Polymers

ABSTRACT

The present invention relates to polymers that include residues of at least one monomer represented by the following Formula (I). With reference to Formula (I), at least one of E1 and E2 independently is, or is independently substituted with, at least one reactive group, such as a (meth)acryloyl group. Monomers represented by Formula (I) and monomer residues thereof have alignment properties, such as photoalignment properties. The present invention also relates to alignment layers that include such polymers, and articles of manufacture, such as optical elements, that include one or more such alignment layers.

FIELD

The present invention relates to polymers that include residues of oneor more monomers having alignment properties, such as photoalignmentproperties, alignment layers containing such polymers, and articles ofmanufacture, such as optical elements, that include such alignmentlayers.

BACKGROUND

Liquid crystal materials are used in various applications. Typically,the liquid crystal materials are formed as a layer over the surface of asubstrate, such as an ophthalmic lens. To obtain desired properties andperformance, the liquid crystal materials of the liquid crystalcontaining layer are typically orientated or aligned along a commondirection. Alignment of the liquid crystal materials can be achieved bycontact of the liquid crystal containing layer with an underlyingalignment layer that includes alignment materials, such as polymers thatcan be aligned. Orientation of the alignment layer can be achieved byphysical methods, such as rubbing, and/or remote methods, such asexposure to electromagnetic radiation.

Alignment of the alignment layer and correspondingly the liquid crystalmaterials of the liquid crystal containing layer by remote methods, suchas by exposure to electromagnetic radiation, can be desirable comparedto physical methods. Physical alignment methods can have associatedtherewith disadvantages, such as dirt pickup by and/or corruption, suchas tearing, of the alignment layer. Remote alignment methods aregenerally not subject to such disadvantages, and can be advantageouslyused to define distinct areas across the alignment layer havingdifferent alignment directions.

It would be desirable to develop new polymers that have alignmentproperties. It would be further desirable that such newly developedpolymers and/or layers containing such polymers, can be remotelyaligned, such as by exposure to electromagnetic radiation.

SUMMARY

In accordance with the present invention, there is provided a polymercomprising at least one residue (or monomer unit) of at least onemonomer represented by the following Formula (I),

With reference to Formula (I): Ring-A is selected from the groupconsisting of aryl and heteroaryl; E is N or C—R¹; and D is selectedfrom the group consisting of O, S, and N—R².

With further reference to Formula (I), R¹ of E and R² of D are eachindependently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, interrupted hydrocarbyl, andsubstituted interrupted hydrocarbyl, wherein each interruptedhydrocarbyl and each substituted interrupted hydrocarbyl are eachindependently interrupted with at least one interrupting group selectedfrom the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—,—N═N—, —N(R₁₁′)— where R₁₁′ is selected from the group consisting ofhydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are each independently 0 to 2,provided that the sum of w and e is 2, and each R₈′ is independentlyselected from the group consisting of hydrogen, hydrocarbyl andsubstituted hydrocarbyl, and combinations of two or more interruptinggroups thereof.

With additional reference to Formula (I), L¹ and L⁴ are eachindependently selected from at least one of: a single bond; —O—; —S—;—C(O)—; —S(O)—; —SO₂—; —N═N—; —N(R₁₁′)— where R₁₁′ is selected from thegroup consisting of hydrogen, hydrocarbyl or substituted hydrocarbyl;—Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are each independently 0 to 2,provided that the sum of w and e is 2, and each R₈′ is independentlyselected from the group consisting of hydrogen, hydrocarbyl andsubstituted hydrocarbyl; hydrocarbyl; substituted hydrocarbyl;interrupted hydrocarbyl; and substituted interrupted hydrocarbyl,wherein each interrupted hydrocarbyl and each substituted interruptedhydrocarbyl are each independently interrupted with at least oneinterrupting group selected from the group consisting of —O—, —S—,—C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ is selectedfrom the group consisting of hydrogen, hydrocarbyl or substitutedhydrocarbyl, —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are eachindependently 0 to 2, provided that the sum of w and e is 2, and eachR₈′ is independently selected from the group consisting of hydrogen,hydrocarbyl and substituted hydrocarbyl, and combinations of two or moreinterrupting groups thereof.

With further reference to Formula (I): t is 0 to 4, or 1 to 4; s is,independently for each g, from 1 to 4; g is 0 to 6, provided that thesum of t and g is at least 1; m is, independently for each t, from 0 to4; and q is, independently for each s, from 0 to 4.

With additional reference to Formula (I), L² independently for each m,and L⁵ independently for each q, are in each case independently selectedfrom the group consisting of divalent linear or branched C₁-C₂₅ alkyl,divalent interrupted linear or branched C₁-C₂₅ alkyl, divalent linear orbranched C₁-C₂₅ perhaloalkyl, divalent interrupted linear or branchedC₁-C₂₅ perhaloalkyl, divalent linear or branched C₂-C₂₅ alkenyl, anddivalent interrupted linear or branched C₂-C₂₅ alkenyl, wherein eachdivalent interrupted linear or branched C₁-C₂₅ alkyl, each divalentinterrupted linear or branched C₁-C₂₅ perhaloalkyl, and each divalentinterrupted linear or branched C₂-C₂₅ alkenyl are each independentlyinterrupted with at least one interrupting group selected from the groupconsisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—,—N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independentlyselected from the group consisting of hydrogen, hydrocarbyl andsubstituted hydrocarbyl, and combinations of two or more interruptinggroups thereof.

With further reference to Formula (I): p is, independently for each t,from 0 to 4, provided the sum of m and p is at least 1 for each t thatis greater than zero; and r is, independently for each s, from 0 to 4,provided the sum of q and r is at least 1 for each s.

With additional reference to Formula (I), L³ independently for each p,and L⁶ independently for each r, are in each case independentlyrepresented by the following Formula (II-1),

With reference to Formula (II-1), Y is, independently for each p andindependently for each r, a divalent linking group selected from thegroup consisting of a single bond, —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—,—S(O)—, —SO₂—, —N(R⁹)—, —N(R⁹)—C(O)—O—, —C(O)—N(R⁹)—, and —Si(R⁹)(R¹⁰)—wherein R⁹ and R¹⁰ are each independently selected from the groupconsisting of hydrogen, hydrocarbyl and substituted hydrocarbyl.

With further reference to Formula (II-1), v and u are eachindependently, for each p and each r, 0 to 5, provided that the sum of vand u is at least 1 for each p that is greater than zero and each r thatis greater than zero.

With additional reference to Formula (II-1), Z is, independently foreach v, a divalent linking group selected from the group consisting of asingle bond, —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—,—N(R⁹)—, —N(R⁹)—C(O)—O—, —C(O)—N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ andR¹⁰ are each independently selected from the group consisting ofhydrogen, hydrocarbyl and substituted hydrocarbyl.

With further reference to Formula (II-1), the divalent rings,

are each independently selected, for each v and each u, from the groupconsisting of divalent aryl, substituted divalent aryl, divalentheteroaryl, substituted divalent heteroaryl, divalent cycloalkyl,substituted divalent cycloalkyl, divalent heterocycloalkyl, andsubstituted divalent heterocycloalkyl.

With reference again to Formula (I), E¹ and E² are each independentlyselected from the group consisting of hydrogen, hydrocarbyl, interruptedhydrocarbyl, substituted hydrocarbyl, and substituted interruptedhydrocarbyl, wherein each interrupted hydrocarbyl and each substitutedinterrupted hydrocarbyl are each independently interrupted with at leastone interrupting group selected from the group consisting of —O—, —S—,—C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, and —Si(R⁹)(R¹⁰)—wherein R⁹ and R¹⁰ are each independently selected from the groupconsisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, andcombinations of two or more interrupting groups thereof.

With regard to E¹ and E² of Formula (I), there is the proviso that atleast one of E¹ and E² independently is, or is independently substitutedwith, at least one reactive group selected from the group consisting of(linear or branched C₁-C₈ alkyl)acryloyl, unsubstituted styrene,substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acidester, unsubstituted cyclic carboxylic acid ester, substituted cycliccarboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl,thiol, amine, isocyanate, aldehyde, and combinations thereof.

With further reference to Formula (I), there are the following furtherprovisos: a direct L¹-L² link between L¹ and L² is free of twoheteroatoms linked together; a direct L¹-L³ link between L¹ and L³ isfree of two heteroatoms linked together; and each direct L²-L³ linkbetween each directly linked L² and L³ is free of two heteroatoms linkedtogether.

With additional reference to Formula (I), there are the followingadditional provisos: a direct L⁴-L⁵ link between L⁴ and L⁵ is free oftwo heteroatoms linked together; a direct L⁴-L⁶ link between L⁴ and L⁶is free of two heteroatoms linked together; and each direct L⁵-L⁶ linkbetween each directly linked L⁵ and L⁶ is free of two heteroatoms linkedtogether.

The features that characterize the present invention are pointed outwith particularity in the claims, which are annexed to and form a partof this disclosure. These and other features of the invention, itsoperating advantages and the specific objects obtained by its use willbe more fully understood from the following detailed description inwhich non-limiting embodiments of the invention are illustrated anddescribed.

DETAILED DESCRIPTION

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subratios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein, unless otherwise indicated, left-to-rightrepresentations of linking groups, such as divalent linking groups, areinclusive of other appropriate orientations, such as, but not limitedto, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup

or equivalently —C(O)O—, is inclusive of the right-to-leftrepresentation thereof,

or equivalently —O(O)C— or —OC(O)—.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asmodified in all instances by the term “about.”

As used herein, molecular weight values of polymers, such as weightaverage molecular weights (Mw) and number average molecular weights(Mn), are determined by gel permeation chromatography using appropriatestandards, such as polystyrene standards.

As used herein, polydispersity index (PDI) values represent a ratio ofthe weight average molecular weight (Mw) to the number average molecularweight (Mn) of the polymer (i.e., Mw/Mn).

As used herein, the term “polymer” means homopolymers (e.g., preparedfrom a single monomer species), copolymers (e.g., prepared from at leasttwo monomer species), and graft polymers.

As used herein, the term “monomer unit” as used in conjunction with theterm polymer and related terms, means a monomer (or residue of amonomer) that has been incorporated into at least a portion of thepolymer.

As used herein, the term “(meth)acrylate” and similar terms, such as“(meth)acrylic acid ester” means methacrylates and/or acrylates. As usedherein, the term “(meth)acrylic acid” means methacrylic acid and/oracrylic acid. As used herein, the term “(linear or branched C₁-C₈alkyl)acryloyl” means (linear or branched C₁-C₈ alkyl)acryloyl and/oracryloyl. As used herein, the term “(meth)acryloyl” means methacryloyland/or acryloyl.

The polymers of the present invention are also referred to herein asalignment polymers and/or alignable polymers.

The polymers of the present invention, as described herein, including,but not limited to, polymers represented by Formula (I) and Formula(VI), in each case can optionally further include one or morecoproducts, resulting from the synthesis of such polymers.

As used herein, the term “actinic radiation” means electromagneticradiation that is capable of causing a response in a material, such as,but not limited to, transforming the polymers of the present inventionfrom a non-aligned arrangement to an aligned arrangement.

As used herein, the term “photochromic” and similar terms, such as“photochromic compound” means having an absorption spectrum for at leastvisible radiation that varies in response to absorption of at leastactinic radiation. Further, as used herein the term “photochromicmaterial” means any substance that is adapted to display photochromicproperties (such as, adapted to have an absorption spectrum for at leastvisible radiation that varies in response to absorption of at leastactinic radiation) and which includes at least one photochromiccompound.

As used herein, the term “photochromic material” includes thermallyreversible photochromic materials and compounds and non-thermallyreversible photochromic materials and compounds. The term “thermallyreversible photochromic compounds/materials” as used herein meanscompounds/materials capable of converting from a first state, forexample a “clear state,” to a second state, for example a “coloredstate,” in response to actinic radiation, and reverting back to thefirst state in response to thermal energy. The term “non-thermallyreversible photochromic compounds/materials” as used herein meanscompounds/materials capable of converting from a first state, forexample a “clear state,” to a second state, for example a “coloredstate,” in response to actinic radiation, and reverting back to thefirst state in response to actinic radiation of substantially the samewavelength(s) as the absorption(s) of the colored state (e.g.,discontinuing exposure to such actinic radiation).

As used herein to modify the term “state,” the terms “first” and“second” are not intended to refer to any particular order orchronology, but instead refer to two different conditions or properties.For purposes of non-limiting illustration, the first state and thesecond state of a photochromic compound can differ with respect to atleast one optical property, such as but not limited to the absorption ofvisible and/or UV radiation. Thus, according to various non-limitingembodiments disclosed herein, the photochromic compounds of the presentinvention can have a different absorption spectrum in each of the firstand second state. For example, while not limiting herein, a photochromiccompound of the present invention can be clear in the first state andcolored in the second state. Alternatively, a photochromic compound ofthe present invention can have a first color in the first state and asecond color in the second state.

As used herein the term “optical” means pertaining to or associated withlight and/or vision. For example, according to various non-limitingembodiments disclosed herein, the optical article or element or devicecan be chosen from ophthalmic articles, elements and devices, displayarticles, elements and devices, windows, mirrors, and active and passiveliquid crystal cell articles, elements and devices.

As used herein the term “ophthalmic” means pertaining to or associatedwith the eye and vision. Non-limiting examples of ophthalmic articles orelements include corrective and non-corrective lenses, including singlevision or multi-vision lenses, which can be either segmented ornon-segmented multi-vision lenses (such as, but not limited to, bifocallenses, trifocal lenses and progressive lenses), as well as otherelements used to correct, protect, or enhance (cosmetically orotherwise) vision, including without limitation, contact lenses,intra-ocular lenses, magnifying lenses, and protective lenses or visors.

As used herein the term “display” means the visible or machine-readablerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements include screens,monitors, and security elements, such as security marks.

As used herein the term “window” means an aperture adapted to permit thetransmission of radiation there-through. Non-limiting examples ofwindows include automotive and aircraft transparencies, windshields,filters, shutters, and optical switches.

As used herein, the term “mirror” means a surface that specularlyreflects a large fraction of incident light.

As used herein, the term “liquid crystal cell” refers to a structurecontaining a liquid crystal material that is capable of being ordered. Anon-limiting example of a liquid crystal cell element is a liquidcrystal display.

As used herein, the term “mesogen” and similar terms, such as “mesogengroup,” “mesogenic,” and “mesogenic group,” means the fundamental unit(or segment or group) of a liquid crystal material that induces, and/oris induced into, structural order amongst and between liquid crystals,such as (but not limited to) liquid crystal materials that are togetherpresent in a liquid crystal composition.

As used herein, spatial or directional terms, such as “left”, “right”,“inner”, “outer”, “above”, “below”, and the like, relate to theinvention as it is depicted in the drawing figures. It is to beunderstood, however, that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting.

As used herein, the terms “formed over,” “deposited over,” “providedover,” “applied over,” residing over,” or “positioned over,” meanformed, deposited, provided, applied, residing, or positioned on but notnecessarily in direct (or abutting) contact with the underlying element,or surface of the underlying element. For example, a layer “positionedover” a substrate does not preclude the presence of one or more otherlayers, coatings, or films of the same or different composition locatedbetween the positioned or formed layer and the substrate.

All documents, such as but not limited to issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

As used herein, the term “a bond” such as used with, but not limited to,L¹, L⁴, Y, and Z, means a single bond.

As used herein, recitations of “linear or branched” groups, such aslinear or branched alkyl, are herein understood to include: a methylenegroup or a methyl group; groups that are linear, such as linear C₂-C₂₀alkyl groups; and groups that are appropriately branched, such asbranched C₃-C₂₀ alkyl groups.

As used herein, recitations of “substituted” group, means a group,including but not limited to, alkyl group, cycloalkyl group,heterocycloalkyl group, aryl group, and/or heteroaryl group, in which atleast one hydrogen thereof has been replaced or substituted with a groupthat is other than hydrogen, such as, but not limited to, halo groups(e.g., F, Cl, I, and Br), hydroxyl groups, ether groups, thiol groups,thio ether groups, carboxylic acid groups, carboxylic acid ester groups,phosphoric acid groups, phosphoric acid ester groups, sulfonic acidgroups, sulfonic acid ester groups, nitro groups, cyano groups,hydrocarbyl groups (including, but not limited to: alkyl; alkenyl;alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl andpolycycloalkyl; heterocycloalkyl; aryl, including hydroxyl substitutedaryl, such as phenol, and including poly-fused-ring aryl; heteroaryl,including poly-fused-ring heteroaryl; and aralkyl groups), and aminegroups, such as —N(R₁₁′)(R₁₂′) where R₁₁′ and R₁₂′ are eachindependently selected, with some embodiments, from hydrogen, linear orbranched C₁-C₂₀ alkyl, C₃-C₁₂ cycloakyl, C₃-C₁₂ heterocycloalkyl, aryl,and heteroaryl.

As used herein, recitations of “halo substituted” and related terms(such as, but not limited to, haloalkyl groups, haloalkenyl groups,haloalkynyl groups, haloaryl groups and halo-heteroaryl groups) means agroup in which at least one, and up to and including all of theavailable hydrogen groups thereof is substituted with a halo group. Theterm “halo-substituted” is inclusive of “perhalo-substituted.” As usedherein, the term perhalo-substituted group and related terms (such as,but not limited to perhaloalkyl groups, perhaloalkenyl groups,perhaloalkynyl groups, perhaloaryl groups and perhalo-heteroaryl groups)means a group in which all of the available hydrogen groups thereof aresubstituted with a halo group. For example, perhalomethyl is —CX₃;perhalophenyl is —C₆X₅, where X represents one or more halo groups, suchas, but not limited to F.

The monomers and monomer residues of the polymers of the presentinvention include groups and sub-groups that can in each case beindependently selected from hydrocarbyl and/or substituted hydrocarbyl.As used herein the term “hydrocarbyl” and similar terms, such as“hydrocarbyl substituent,” means: linear or branched C₁-C₂₅ alkyl (e.g.,linear or branched C₁-C₁₀ alkyl); linear or branched C₂-C₂₅ alkenyl(e.g., linear or branched C₂-C₁₀ alkenyl); linear or branched C₂-C₂₅alkynyl (e.g., linear or branched C₂-C₁₀ alkynyl); C₃-C₁₂ cycloalkyl(e.g., C₃-C₁₀ cycloalkyl); C₃-C₁₂ heterocycloalkyl (having at least onehetero atom in the cyclic ring); C₅-C₁₈ aryl (including polycyclic arylgroups) (e.g., C₅-C₁₀ aryl); C₅-C₁₈ heteroaryl (having at least onehetero atom in the aromatic ring); and C₆-C₂₄ aralkyl (e.g., C₆-C₁₀aralkyl).

Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representativealkenyl groups include but are not limited to vinyl, allyl and propenyl.Representative alkynyl groups include but are not limited to ethynyl,1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representativecycloalkyl groups include but are not limited to cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents.Representative heterocycloalkyl groups include but are not limited toimidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl.Representative aryl groups include but are not limited to phenyl,naphthyl, anthracynyl and triptycenyl. Representative heteroaryl groupsinclude but are not limited to furanyl, pyranyl, pyridinyl,isoquinoline, and pyrimidinyl. Representative aralkyl groups include butare not limited to benzyl, and phenethyl.

The term “substituted hydrocarbyl” as used herein means a hydrocarbylgroup in which at least one hydrogen thereof has been substituted with agroup that is other than hydrogen, such as, but not limited to, halogroups, hydroxyl groups, ether groups, thiol groups, thio ether groups,carboxylic acid groups, carboxylic acid ester groups, phosphoric acidgroups, phosphoric acid ester groups, sulfonic acid groups, sulfonicacid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g.,alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl,and aralkyl groups), and amine groups, such as —N(R₁₁′)(R₁₂′) where R₁₁′and R₁₂′ are each independently selected from hydrogen, hydrocarbyl andsubstituted hydrocarbyl.

The term “substituted hydrocarbyl” is inclusive of halohydrocarbyl (orhalo substituted hydrocarbyl) substituents. The term “halohydrocarbyl”as used herein, and similar terms, such as halo substituted hydrocarbyl,means that at least one hydrogen atom of the hydrocarbyl (e.g., of thealkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl,and aralkyl groups) is replaced with a halogen atom selected fromchlorine, bromine, fluorine and iodine. The degree of halogenation canrange from at least one hydrogen atom but less than all hydrogen atomsbeing replaced by a halogen atom (e.g., a fluoromethyl group), to fullhalogenation (perhalogenation) in which all replaceable hydrogen atomson the hydrocarbyl group have each been replaced by a halogen atom(e.g., trifluoromethyl or perfluoromethyl). Correspondingly, the term“perhalohydrocarbyl group” as used herein means a hydrocarbyl group inwhich all replaceable hydrogens have been replaced with a halogen.Examples of perhalohydrocarbyl groups include, but are not limited to,perhalogenated phenyl groups and perhalogenated alkyl groups.

The hydrocarbyl and substituted hydrocarbyl groups from which thevarious groups described herein can each be independently selected, insome instances and with some embodiments, can in each case beindependently interrupted with at least one interrupting group, and whenso interrupted are referred to herein as interrupted hydrocarbyl andsubstituted interrupted hydrocarbyl groups. Each interrupted hydrocarbyland each substituted interrupted hydrocarbyl, are in each caseindependently interrupted with at least one interrupting group selectedfrom —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— whereR₁₁′ in each case is independently selected from hydrogen, hydrocarbylor substituted hydrocarbyl, —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e areeach independently selected from 0 to 2, provided that the sum of w andt is 2, and each R₈′ is independently selected from hydrogen,hydrocarbyl and substituted hydrocarbyl, and combinations of two or moreinterrupting groups thereof. As used herein, by interrupted with atleast one interrupting group selected from —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— and —Si(OR₈′)_(w)(R₈′)_(e)—, means thatat least one carbon of, but less than all of the carbons of, theinterrupted hydrocarbyl group or substituted interrupted hydrocarbylgroup, is in each case independently replaced with one or more of therecited divalent non-carbon linking groups. The interrupted hydrocarbyland substituted interrupted hydrocarbyl groups can be interrupted withtwo or more of the above recited linking groups, which can be adjacentto each other or separated by one or more carbons. For purposes ofnon-limiting illustration, a combination of adjacent —C(O)— and—N(R₁₁′)— can provide a divalent amide linking or interrupting group,—C(O)—N(R₁₁′)—. For purposes of further non-limiting illustration, acombination of adjacent —N(R₁₁′)—, —C(O)— and —O— can provide a divalentcarbamate (or urethane) linking or interrupting group, —N(R₁₁′)—C(O)—O—,where R₁₁′ is hydrogen.

The term “interrupted with” as used with regard to the various groupsdescribed herein, such as but not limited to interrupted hydrocarbyl andsubstituted interrupted hydrocarbyl groups, also includes interruptionat the initial linking position of the group to the compound or corecompound structure with at least one interrupting group selected from—O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ ineach case is independently selected from hydrogen, hydrocarbyl orsubstituted hydrocarbyl, —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are eachindependently selected from 0 to 2, provided that the sum of w and t is2, and each R₈′ is independently selected from hydrogen, hydrocarbyl andsubstituted hydrocarbyl, and combinations of two or more interruptinggroups thereof. For purposes of nonlimiting illustration, when an R¹ (ofC—R¹ of E) of Formula (I) is interrupted hydrocarbyl, the R¹ interruptedhydrocarbyl group can be interrupted with one or more of the aboverecited divalent interrupting groups, such as but not limited to —O—:(i) along the hydrocarbyl chain thereof; and/or (ii) at the point whereR¹ is bonded to the C of C—R¹.

The term “alkyl” as used herein, in accordance with some embodiments,means linear or branched alkyl, such as but not limited to, linear orbranched C₁-C₂₅ alkyl, or linear or branched C₁-C₁₀ alkyl, or linear orbranched C₂-C₁₀ alkyl. Examples of alkyl groups from which the variousalkyl groups of the present invention can be selected from, include, butare not limited to, those recited previously herein. Alkyl groups of thevarious compounds of the present invention can, with some embodiments,include one or more unsaturated linkages selected from —CH═CH— groupsand/or one or more —C≡C— groups, provided the alkyl group is free of twoor more conjugated unsaturated linkages. With some embodiments, thealkyl groups are free of unsaturated linkages, such as —CH═CH— groupsand —C≡C— groups.

The term “cycloalkyl” as used herein, in accordance with someembodiments, means groups that are appropriately cyclic, such as but notlimited to, C₃-C₁₂ cycloalkyl (including, but not limited to, cyclicC₅-C₇ alkyl) groups. Examples of cycloalkyl groups include, but are notlimited to, those recited previously herein. The term “cycloalkyl” asused herein in accordance with some embodiments also includes: bridgedring polycycloalkyl groups (or bridged ring polycyclic alkyl groups),such as but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) andbicyclo[2.2.2]octyl; and fused ring polycycloalkyl groups (or fused ringpolycyclic alkyl groups), such as, but not limited to,octahydro-1H-indenyl, and decahydronaphthalenyl.

The term “heterocycloalkyl” as used herein, in accordance with someembodiments, means groups that are appropriately cyclic, such as but notlimited to, C₃-C₁₂ heterocycloalkyl groups or C₅-C₇ heterocycloalkylgroups, and which have at least one hetero atom in the cyclic ring, suchas, but not limited to, O, S, N, P, and combinations thereof. Examplesof heterocycloalkyl groups include, but are not limited to, thoserecited previously herein. The term “heterocycloalkyl” as used herein,in accordance with some embodiments, also includes: bridged ringpolycyclic heterocycloalkyl groups, such as but not limited to,7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclic heterocycloalkylgroups, such as but not limited to, octahydrocyclopenta[b]pyranyl, andoctahydro-1H-isochromenyl.

The term “heteroaryl,” as used herein, in accordance with someembodiments, includes but is not limited to C₅-C₁₈ heteroaryl, such asbut not limited to C₅-C₁₀ heteroaryl (including fused ring polycyclicheteroaryl groups) and means an aryl group having at least one heteroatom in the aromatic ring, or in at least one aromatic ring in the caseof a fused ring polycyclic heteroaryl group. Examples of heteroarylgroups include, but are not limited to, those recited previously herein.

As used herein, the term “fused ring polycyclic-aryl-alkyl group” andsimilar terms such as, fused ring polycyclic-alkyl-aryl group, fusedring polycyclo-aryl-alkyl group, and fused ring polycyclo-alkyl-arylgroup means a fused ring polycyclic group that includes at least onearyl ring and at least one cycloalkyl ring that are fused together toform a fused ring structure. For purposes of non-limiting illustration,examples of fused ring polycyclic-aryl-alkyl groups include, but are notlimited to indenyl, 9H-flourenyl, cyclopentanaphthenyl, and indacenyl.

The term “aralkyl,” as used herein, and in accordance with someembodiments, includes but is not limited to C₆-C₂₄ aralkyl, such as butnot limited to C₆-C₁₀ aralkyl, and means an aryl group substituted withan alkyl group. Examples of aralkyl groups include, but are not limitedto, those recited previously herein.

The polymers and related monomers according to the present invention,such as, but not limited to the monomers represented by Formula (I), andthe various groups thereof are described in further detail herein asfollows.

In accordance with some embodiments, and with reference to Formula (I):Ring-A is aryl; and R¹ of E and R² of D are each independently selectedfrom hydrogen, linear or branched C₁-C₂₅ alkyl, linear or branchedC₂-C₂₅ alkenyl, C₃-C₁₂ cycloalkyl, C₃-C₁₂ heterocycloalkyl, aryl, andheteroaryl.

In accordance with some embodiments, and with reference to Formula (I):m is at least 1 for at least one t; q is at least 1 for at least one s.

With further reference to Formula (I) and with some embodiments, L² is,independently for each m, and L⁵ is, independently for each q, in eachcase independently selected from divalent linear or branched C₁-C₂₅alkyl, divalent interrupted linear or branched C₁-C₂₅ alkyl, divalentlinear or branched C₁-C₂₅ perhaloalkyl, and divalent interrupted linearor branched C₁-C₂₅ perhaloalkyl, where each divalent interrupted linearor branched C₁-C₂₅ alkyl and each divalent interrupted linear orbranched C₁-C₂₅ perhaloalkyl are each independently interrupted with atleast one interrupting group selected from the interrupting groups —O—,—C(O)O—, and —OC(O)O—.

With additional reference to Formula (I) and with some embodiments: p isat least 1 for at least one t; r is at least 1 for at least one s.

With additional reference to Formula (I) and with some embodiments, L³independently for each p, and L⁶ independently for each r, are in eachcase independently represented by the following Formula (II-2),

With reference to Formula (II-2), and with some embodiments, thedivalent rings,

are each independently selected, for each v and each u, fromphenylen-1,4-diyl, substituted phenylen-1,4-diyl, cyclohexan-1,4-diyl,substituted cyclohexan-1,4-diyl, pyrimidin-2,5-diyl, substitutedpyrimidin-2,5-diyl, pyridine-2,5-diyl, substituted pyridine-2,5-diyl,naphthalene-2,6-diyl, substituted naphthalene-2,6-diyl,1,2,3,4-tetrahydronaphthalene-2,6-diyl,1,2,3,4-tetrahydronaphthalene-2,6-diyl in which the aromatic ring issubstituted, decahydronaphthalene-2,6-diyl, indane-2,5(6)-diyl,fluorene-2,-7-diyl, phenanthrene-2,7-diyl,9,10-dihydrophenanthrene-2,7-diyl, (1,3,4)thiadiazol-2,5-diyl,(1,3)thiazol-2,5-diyl, (1,3)thiazol-2,4-diyl, thiophen-2,4-diyl,thiophen-2,5-diyl, (1,3)dioxan-2,5-diyl, piperidin-1,4-diyl, and,piperazin-1,4-diyl.

With reference to Formula (I), and with some embodiments, E¹ and E² areeach independently selected from hydrogen, linear or branched C₁-C₂₅alkyl, interrupted linear or branched C₁-C₂₅ alkyl, linear or branchedC₂-C₂₅ alkenyl, and interrupted linear or branched C₂-C₂₅ alkenyl,wherein each interrupted linear or branched C₁-C₂₅ alkyl and eachinterrupted linear or branched C₂-C₂₅ alkenyl are each independentlyinterrupted with at least one interrupting group selected from —O—, —S—,and —C(O)O—.

With regard to E¹ and E² of Formula (I), there is the further proviso,with some embodiments, that E¹ and/or E² independently is, or isindependently substituted with, at least one reactive group selectedfrom (meth)acryloyl, unsubstituted styrene, substituted styrene,oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstitutedcyclic carboxylic acid ester, substituted cyclic carboxylic acid ester,cyclic carboxylic acid anhydride, hydroxyl, thiol, and combinationsthereof.

With some embodiments, Ring-A of Formula (I) is phenyl, and the monomerrepresented by Formula (I) is further represented by the followingFormula (I-A):

With reference to Formula (I-A), g is from 0 to 4, provided that the sumof t and g is at least 1. The groups and subscripts of Formula (I-A) areeach as described previously herein with reference to Formula (I), andas described further herein.

With reference to Formula (I), and correspondingly Formula (I-A), R¹ ofE and R² of D, with some embodiments, are each independently selectedfrom hydrogen and linear or branched C₁-C₁₀ alkyl.

With further reference to Formula (I), and correspondingly Formula(I-A), L² is, independently for each m, and L⁵ is, independently foreach q, in each case independently selected from divalent linear orbranched C₁-C₁₀ alkyl, divalent interrupted linear or branched C₁-C₁₀alkyl, divalent linear or branched C₁-C₁₀ perfluoroalkyl, and divalentinterrupted linear or branched C₁-C₁₀ perfluoroalkyl, where eachdivalent interrupted linear or branched C₁-C₁₀ alkyl and each divalentinterrupted linear or branched C₁-C₁₀ perfluoroalkyl are eachindependently interrupted with at least one interrupting group selectedfrom —O—, —C(O)O—, and —OC(O)O—.

With additional reference to Formula (I), and correspondingly Formula(I-A), independently for each L³, and independently for each L⁶, Z is,independently for each v, selected from the group consisting of a singlebond, —O— and —C(O)O—.

With further additional reference to Formula (I), and correspondinglyFormula (I-A), and independently for each L³, and independently for eachL⁶, the divalent rings,

are each independently selected, for each v and each u, fromphenylen-1,4-diyl, substituted phenylen-1,4-diyl, cyclohexan-1,4-diyl,and substituted cyclohexan-1,4-diyl.

With further reference to Formula (I), and correspondingly Formula(I-A), and in accordance with some embodiments, E¹ and E² are eachindependently selected from hydrogen, linear or branched C₁-C₁₀ alkyl,and interrupted linear or branched C₁-C₁₀ alkyl, where each interruptedlinear or branched C₁-C₁₀ alkyl is independently interrupted with atleast one interrupting group selected from —O—, —S—, and —C(O)O—.

With regard to E¹ and E² of Formula (I), and correspondingly Formula(I-A), there is the further proviso, with some embodiments, that atleast one of E¹ and E² independently is, or is independently substitutedwith, at least one reactive group selected from the group consisting of(meth)acryloyl, unsubstituted styrene, substituted styrene, oxirane,thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cycliccarboxylic acid ester, substituted cyclic carboxylic acid ester, cycliccarboxylic acid anhydride, hydroxyl, thiol, and combinations thereof.

In accordance with some embodiments and with reference to Formula (I),and correspondingly Formula (I-A), E¹ and E² are each independentlyselected from hydrogen, linear or branched C₁-C₁₀ alkyl, and interruptedlinear or branched C₁-C₁₀ alkyl, where each interrupted linear orbranched C₁-C₁₀ alkyl is independently interrupted with at least oneinterrupting group selected from —O— and —C(O)O—. With regard to E¹ andE² of Formula (I), and correspondingly Formula (I-A), there is thefurther proviso, with some embodiments, at least one of E¹ and E²independently is, or is independently substituted with, (meth)acryloyl.

For purposes of non-limiting illustration, and in accordance with someembodiments of the present invention, each E¹ and each E² are in eachcase independently represented by the following Formula (VII),

(X*)_(n)-(L*)-  (VII)

With reference to Formula (VII), L* is selected from a bond, such as asingle bond, multivalent hydrocarbyl, multivalent substitutedhydrocarbyl, multivalent interrupted hydrocarbyl, and multivalentsubstituted interrupted hydrocarbyl, where each multivalent interruptedhydrocarbyl and each multivalent substituted interrupted hydrocarbyl areeach independently interrupted with at least one interrupting groupselected from —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—,—N(R⁹)—, and —Si(R⁹)(R¹⁰)— where R⁹ and R¹⁰ are each independentlyselected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, andcombinations of two or more interrupting groups thereof.

With further reference to Formula (VII), subscript n in each case isindependently at least 1, such as 1 to 10, or 1 to 8, or 1 to 6, or 1 to5, or 1 to 4, or 1 to 3, or 2, or 1.

With additional reference to Formula (VII), X* in each case andindependently for each n is a reactive group selected from (linear orbranched C₁-C₈ alkyl)acryloyl, unsubstituted styrene, substitutedstyrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester,unsubstituted cyclic carboxylic acid ester, substituted cycliccarboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl,thiol, amine, isocyanate, aldehyde, and combinations thereof. Withfurther additional reference to Formula (VII), there is the proviso thatfor at least one of E¹ and E², at least one X* is selected from areactive group.

In accordance with some embodiments, the polymer of the presentinvention further includes at least one residue of an additional monomerselected from (meth)acrylic acid, hydrocarbyl (meth)acrylate,substituted hydrocarbyl (meth)acrylate, unsubstituted styrene,substituted styrene, and combinations thereof.

With reference to Formula (I), and correspondingly Formula (I-A), and inaccordance with some further embodiments, D is O.

With reference to Formula (I), and with some embodiments of the presentinvention, L¹ and L⁴ are each independently selected from t one of thefollowing Formulas IIIa, IIIb, IIIc, IIId, IIIe, or IIIf:

where R⁷ is selected from hydrocarbyl and substituted hydrocarbyl,

where R⁸ is selected from hydrocarbyl and substituted hydrocarbyl,

where R^(b) is selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and

where R^(c) and R^(d) are each independently selected from hydrogen,hydrocarbyl and substituted hydrocarbyl.

With reference to Formulas IIIb and IIId above, R⁷ and R⁸ for each of L¹and L⁴ are each independently selected from divalent linear or branchedC₁-C₂₅ alkyl, divalent linear or branched C₂-C₂₅ alkenyl, divalentC₃-C₁₂ cycloalkyl, divalent C₃-C₁₂ heterocycloalkyl, divalent aryl, anddivalent heteroaryl.

In accordance with some embodiments, L¹ and L⁴ of Formula (I) are eachindependently the divalent linking group represented by Formula IIId,and each R⁸ is independently a divalent linear or branched C₁-C₈ alkylgroup.

With reference to Formulas IIIe and IIIf above, and in accordance withsome embodiments, R^(b), R^(c), and R^(d) for each of L¹ and L⁴ are eachindependently selected from linear or branched C₁-C₂₅ alkyl, linear orbranched C₂-C₂₅ alkenyl, C₃-C₁₂ cycloalkyl, C₃-C₁₂ heterocycloalkyl,aryl, and heteroaryl.

With further reference to Formulas IIIe and IIIf above, and inaccordance with some further embodiments, R^(b), R^(c), and R^(d) foreach of L¹ and L⁴ are each independently a linear or branched C₁-C₈alkyl group.

With some embodiments of the present invention and with reference toFormula (I) and Formula (II-1), divalent Ring-(B) and divalent Ring-(C),are each independently selected from the group consisting of divalentaryl, substituted divalent aryl, divalent heteroaryl, and substituteddivalent heteroaryl.

In accordance with some further embodiments of the present invention andwith reference to Formula (I) and Formula (II-2), divalent Ring-(B) anddivalent Ring-(C), are each independently selected from the groupconsisting of phenylen-1,4-diyl, substituted phenylen-1,4-diyl,pyrimidin-2,5-diyl, substituted pyrimidin-2,5-diyl, pyridine-2,5-diyl,substituted pyridine-2,5-diyl, naphthalene-2,6-diyl, substitutednaphthalene-2,6-diyl, and phenanthrene-2,7-diyl.

With some embodiments of the polymer of the present invention and withreference to Formula (I), each L³ and each L⁶, are in each caseindependently a divalent group selected from the following Formulas,IV(A) through IV(O):

In accordance with some embodiments of the polymers of the presentinvention and with reference to Formula (I), at least one of L³ and L⁶independently is a mesogenic group, and the polymer is a mesogenicpolymer. Since the polymers of the present invention, with someembodiments, include at least one residue of at least one monomerrepresented by Formula (I), and at least one of L³ and L⁶ independentlyis a mesogenic group, the polymers of the present invention can bedescribed as mesogenic polymers when at least one of L³ and L⁶independently is a mesogenic group.

Non-limiting examples of monomers, such as represented by Formula (I),from which the polymers of the present invention can be prepared,include those represented by the following Formulas (M-1) to (M-17):

The polymers of the present invention, with some embodiments, include atleast one residue of at least one further monomer represented by thefollowing Formula (V),

E³(L³)_(p)-(L²)_(m)_(t′)L¹-E⁴  Formula (V)

With reference to Formula (V): t′ is from 1 to 4; L¹, L², and L³, areeach independently as described previously herein with reference toFormula (I); m is, independently for each t′, from 0 to 4; p is,independently for each t′, from 0 to 4, provided that the sum of m and pis at least one for each t′.

With further reference to Formula (V), E³ and E⁴ are each independentlyselected from hydrogen, hydrocarbyl, interrupted hydrocarbyl,substituted hydrocarbyl, and substituted interrupted hydrocarbyl, whereeach interrupted hydrocarbyl and each substituted interruptedhydrocarbyl are each independently interrupted with at least oneinterrupting group selected from —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—,—S(O)—, —SO₂—, —N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are eachindependently selected from the group consisting of hydrogen,hydrocarbyl and substituted hydrocarbyl, and combinations of two or moreinterrupting groups thereof.

With additional reference to Formula (V), there is the proviso that E³is, or is substituted with, at least one reactive group selected from(linear or branched C₁-C₈ alkyl)acryloyl, unsubstituted styrene,substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acidester, unsubstituted cyclic carboxylic acid ester, substituted cycliccarboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl,thiol, amine, isocyanate, aldehyde, and combinations thereof.

With some embodiments, E³ of Formula (V) is independently represented byFormula (VII) as described previously and independently herein withregard to E¹ and E² of Formula (I).

The polymers of the present invention, with some embodiments, include atleast one polymer segment represented by the following Formula (VI),

With reference to Formula (VI): E^(1a) independently for each x is adivalent residue of E¹ of Formula (I): E^(2a) independently for each yis a divalent residue of E² of Formula (I); and E^(3a) independently foreach z is a divalent residue of E³ of Formula (V).

With further reference to Formula (VI): h is from 1 to 10,000; x is from0 to 10 for each h; y is from 0 to 10 for each h; and z is from 0 to 10for each h. With additional reference to Formula (VI), there is: (i) theproviso that the sum of x, y, and z is at least one for each h; and (ii)the further proviso that the sum of x and y is at least one for at leastone h.

The polymers of the present invention can, with some embodiments, beselected from linear polymers, branched polymers, star polymers, graftpolymers, and mixtures thereof.

Each polymer segment represented by Formula (VI) can independently havea chain architecture (or chain structure) selected from: random chainarchitecture (in which the monomer residues are distributed randomlyalong the polymer segment); block chain architecture (in which themonomer residues are distributed in blocks along the polymer segment);gradient chain architecture (in which the monomer residues aredistributed in a gradient along the polymer segment); and combinationsof two or more such chain architectures.

With reference to Formula (VI), and in accordance with some embodiments,E^(1a), E^(2a), and E^(3a) are each independently a residue of aradically polymerizable group, and at least the polymer segmentrepresented by Formula (VI) is prepared by art-recognized radicalpolymerization methods, such as, but not limited to, free radicalpolymerization methods, and living radical polymerization methods, suchas atom transfer radical polymerization methods. With some embodimentsof the present invention, E^(1a), E^(2a), and E^(3a) are eachindependently a residue of a (meth)acryloyl group.

The polymers of the present invention include at least one polymer chainsegment represented by Formula (VI) as described above. The polymerchain segment represented by Formula (VI) can represent one or moresegments that form (or define) at least a portion of the chain, orbackbone, architecture of the polymer. With some embodiments, thepolymer chain segment represented by Formula (VI) is located in at leastone of: the backbone of the polymer; one or more branches of the polymer(when the polymer is branched); and one or more arms of the polymer(when the polymer has star or comb architecture).

With some embodiments, the polymer of the present invention includes atleast one polymer chain segment represented by Formula (VI), such as 1to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1to 3 polymer chain segments represented by Formula (VI).

The polymers of the present invention can have any suitable molecularweight. With some embodiments, the polymers of the present inventionhave a Mw of from 5,000 to 2,500,000, or from 10,000 to 500,000, or from30,000 to 200,000; and an Mn of from 1,000 to 1,000,000, or from 5,000to 250,000, or from 20,000 to 80,000. The polymers of the presentinvention, with some embodiments, have a polydispersity index(PDI=Mw/Mn) of at least 1.0, such as from 1.0 to 3.5, or from 1.5 to3.5, or from 2.0 to 3.0.

The present invention also related to an alignment layer that includesat least one polymer of the present invention, such as described hereinwith reference to Formula (I).

As used herein the term “alignment layer” means a layer that canfacilitate the positioning of one or more other structures that areexposed, directly and/or indirectly, to at least a portion thereof. Asused herein the term “order” means bringing into a suitable arrangementor position, such as aligning with another structure or material, or bysome other force or effect. Thus, as used herein the term “order”encompasses both: (i) contact methods of ordering a material, such as byaligning with another structure or material; and (ii) non-contactmethods of ordering a material, such as by exposure to an external forceor effect. The term order also encompasses combinations of contact andnon-contact methods.

For purposes of non-limiting illustration, liquid crystal materials,dichroic compounds, and/or photochromic-dichroic compounds that are atleast partially aligned by interaction with the alignment layer, can beat least partially aligned such that the long-axis of the liquid crystalmaterials, dichroic compounds, and/or photochromic-dichroic compounds(such as in an activated state) are essentially parallel to at least thefirst general direction of the alignment layer. With some embodiments,the liquid crystal materials, dichroic compounds, and/orphotochromic-dichroic compounds that are at least partially aligned byinteraction with the alignment layer are bound to or reacted with thealignment layer. As used herein with reference to order or alignment ofa material or structure, the term “general direction” refers to thepredominant arrangement or orientation of the material, compound orstructure. Further, it will be appreciated by those skilled in the artthat a material, compound or structure can have a general direction eventhough there is some variation within the arrangement of the material,compound or structure, provided that the material, compound or structurehas at least one predominate arrangement.

The alignment layer of the present invention can, with some embodiments,have at least a first general direction. For example, the alignmentlayer of the present invention can include a first ordered region havinga first general direction and at least one second ordered regionadjacent the first ordered region having a second general direction thatis different from the first general direction. Further, the alignmentlayer of the present invention can have a plurality of regions, each ofwhich has a general direction that is the same or different from theremaining regions so as to form a desired pattern or design.

The alignment layer of the present invention can, with some embodiments,be a crosslinked alignment layer, a non-crosslinked alignment layer(such as, but not limited to, a thermoplastic alignment layer), andcombinations thereof. With some embodiments, the alignment layer of thepresent invention can be in the form of a film (such as formed from athermoplastic coating composition and/or a crosslinkable coatingcomposition), a sheet (such as formed by extrusion of a thermoplasticextrusion composition and/or a crosslinkable extrusion composition), andcombinations thereof.

The alignment layer of the present invention can be aligned byart-recognized methods including, but not limited to, contact methods(such as by a shear force), and non-contact methods (such as by exposureto a magnetic field, an electric field, and/or linearly polarizedradiation). With some embodiments, the alignment layer is in the form ofa sheet, which can be aligned by uniaxial stretching and/or duringextrusion of the sheet.

The present invention also relates to an article of manufacture thatincludes the alignment layer of the present invention, which residesover at least a portion of at least one surface of the article ofmanufacture.

With some embodiments, the article of manufacture is an optical elementthat includes: an optical substrate; and in which the alignment layerresides over at least a portion of a surface of the optical substrate.

The alignment layer can be formed over the optical substrate inaccordance with art-recognized methods including, but not limited to,spin application methods, spray application methods, curtain coatingmethods, draw-down application methods (such as using a doctor-bladeand/or draw-down bar), lamination methods (such as with preformed filmsand/or sheets), extrusion methods, in-mold coating (or injection)methods, and combinations of two or more such methods thereof.

The optical substrate, of the optical elements of the present inventioncan, with some embodiments, be formed from, and correspondingly include,organic materials, inorganic materials, or combinations thereof (forexample, composite materials).

Examples of organic materials that can be used as optical substrates ofthe optical elements of the present invention, include polymericmaterials, such as homopolymers and copolymers, prepared from themonomers and mixtures of monomers disclosed in U.S. Pat. No. 5,962,617and in U.S. Pat. No. 5,658,501 from column 15, line 28 to column 16,line 17. For example, such polymeric materials can be thermoplastic orthermoset polymeric materials, can be transparent or optically clear,and can have any refractive index required. Examples of such monomersand polymers include: polyol(allyl carbonate) monomers, e.g., allyldiglycol carbonates such as diethylene glycol bis(allyl carbonate),which monomer is sold under the trademark CR-39 by PPG Industries, Inc.;polyurea-polyurethane (polyurea-urethane) polymers, which are prepared,for example, by the reaction of a polyurethane prepolymer and a diaminecuring agent, a composition for one such polymer being sold under thetrademark TRIVEX by PPG Industries, Inc.; polyol(meth)acryloylterminated carbonate monomer; diethylene glycol dimethacrylate monomers;ethoxylated phenol methacrylate monomers; diisopropenyl benzenemonomers; ethoxylated trimethylol propane triacrylate monomers; ethyleneglycol bismethacrylate monomers; poly(ethylene glycol) bismethacrylatemonomers; urethane acrylate monomers; poly(ethoxylated bisphenol Adimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); poly(vinylchloride); poly(vinylidene chloride); polyethylene; polypropylene;polyurethanes; polythiourethanes; thermoplastic polycarbonates, such asthe carbonate-linked resin derived from bisphenol A and phosgene, onesuch material being sold under the trademark LEXAN; polyesters, such asthe material sold under the trademark MYLAR; poly(ethyleneterephthalate); polyvinyl butyral; poly(methyl methacrylate), such asthe material sold under the trademark PLEXIGLAS, and polymers preparedby reacting polyfunctional isocyanates with polythiols or polyepisulfidemonomers, either homopolymerized or co- and/or terpolymerized withpolythiols, polyisocyanates, polyisothiocyanates and optionallyethylenically unsaturated monomers or halogenated aromatic-containingvinyl monomers. Also contemplated are copolymers of such monomers andblends of the described polymers and copolymers with other polymers, forexample, to form block copolymers or interpenetrating network products.

Examples of inorganic materials that can be used as optical substrateswith some embodiments of the present invention include, but are notlimited to, glasses, minerals, ceramics, and metals. With someembodiments, the optical substrate can include glass. In otherembodiments, the optical substrate can have a reflective surface, forexample, a polished ceramic substrate, metal substrate, or mineralsubstrate. In other embodiments, a reflective coating or layer (e.g., ametal layer, such as a silver layer) can be deposited or otherwiseapplied to a surface of an inorganic or an organic substrate to make itreflective or to enhance its reflectivity.

The alignment layer of the optical element, with some embodiments, is atleast partially aligned by exposing at least a portion of the alignmentlayer to at least one of, a magnetic field, an electric field, linearlypolarized radiation, and shear force, in each case in accordance withart-recognized methods.

The optical element, with some embodiments, is selected from anophthalmic element, a display element, a window, a mirror, and a liquidcrystal cell element.

The optical element, with some further embodiments, is an ophthalmicelement, which is selected from a corrective lens, a non-correctivelens, a contact lens, an intra-ocular lens, a magnifying lens, aprotective lens, and a visor.

The optical element, with some embodiments, includes over at least aportion of the surface of the optical substrate, at least one additionallayer, where each additional layer is independently selected from aprimer layer, a protective layer, an anti-reflective layer, a reflectivelayer, a polarizing layer, a photochromic layer, a liquid crystal layer,and combinations thereof.

Primer layers, protective layers, anti-reflective layers, reflectivelayers, polarizing layers, photochromic layers, and liquid crystallayers of the optical elements of the present invention can eachindependently include organic matrices and/or inorganic matrices,including those as described previously herein, and can be formed inaccordance with art-recognized methods including those methods describedpreviously herein.

The optional primer coating layer can include a single layer or multiplelayers, each having the same or a different composition. The optionalprimer layer typically includes an organic matrix, such as athermoplastic organic matrix and/or a crosslinked organic matrix.Additionally or alternatively to an organic matrix, the optional primerlayer can include an inorganic matrix, including, for example, silanelinkages, siloxane linkages and/or titanate linkages. With someembodiments, the organic matrix of the optional primer layer includes,for example: acrylate residues (or monomer units) and/or methacrylateresidues; vinyl residues; ether linkages; sulfide linkages, includingmonosulfide linkages and/or polysulfide linkages; carboxylic esterlinkages; carbonate linkages (e.g., —O—C(O)—O—) urethane linkages (e.g.,—N(H)—C(O)—O—); carbon-carbon linkages; and/or thiourethane linkages(e.g., —N(H)—C(O)—S—).

Typically, the optional primer layer is formed from a primer coatingcomposition. The primer coating composition can be a curable primercoating composition, that is curable by exposure to, for example:ambient temperatures, such as in the case of two component coatingcompositions; elevated temperatures (e.g., 80° C. to 150° C. for 5 to 60minutes), such as in the case of thermally cured coating compositions;or actinic radiation, such as in the case of ultraviolet light curablecoating compositions.

The optional primer layer can have any suitable thickness. With someembodiments, the optional primer layer has a thickness of from 0.5microns to 20 microns, such as from 1 to 10 microns, or from 2 to 8microns, or from 3 to 5 microns, inclusive of the recited values.

The optional protective layer is, with some embodiments, selected froman abrasion-resistant coating, such as a “hard coat.” Each protectivelayer can include a single layer or multiple layers, each having thesame or a different composition. The optional protective layer can beselected from abrasion-resistant coatings including organo silanes,abrasion-resistant coatings including radiation-cured acrylate-basedthin films, abrasion-resistant coatings based on inorganic materialssuch as silica, titania and/or zirconia, organic abrasion-resistantcoatings of the type that are ultraviolet light curable, oxygenbarrier-coatings, UV-shielding coatings, and combinations thereof. Withsome embodiments, the optional protective layer is a hard coat layerthat includes a first layer of a radiation-cured acrylate-based thinfilm and a second layer including an organo-silane. Non-limitingexamples of commercially available hard coating products includeCRYSTALCOAT® abrasion-resistant coatings, commercially available fromSDC Coatings, Inc., and HI-GARD® coatings, commercially available fromPPG Industries, Inc.

The optional protective layer can be selected from art-recognized hardcoat materials, such as organo-silane abrasion-resistant coatings.Organo-silane abrasion-resistant coatings, often referred to as hardcoats or silicone-based hard coatings, are well known in the art, andare commercially available from various manufacturers, such as SDCCoatings, Inc. and PPG Industries, Inc. Reference is made to U.S. Pat.No. 4,756,973 at column 5, lines 1-45; and to U.S. Pat. No. 5,462,806 atcolumn 1, lines 58 through column 2, line 8, and column 3, line 52through column 5, line 50, which disclosures describe organo-silane hardcoatings and which disclosures are incorporated herein by reference.Reference is also made to U.S. Pat. Nos. 4,731,264, 5,134,191, 5,231,156and International Patent Publication WO 94/20581 for disclosures oforgano-silane hard coatings, which disclosures are also incorporatedherein by reference. The hard coat layer can be applied by those coatingmethods as described previously herein with regard to the alignmentlayer, such as spin coating.

Other coatings that can be used to form the optional protective layer,include, but are not limited to, polyfunctional acrylic hard coatings,melamine-based hard coatings, urethane-based hard coatings, alkyd-basedcoatings, silica sol-based hard coatings or other organic orinorganic/organic hybrid hard coatings.

The optional protective layer, with some embodiments, is selected fromart-recognized organo-silane type hard coatings. Organo-silane type hardcoatings from which the optional protective coating layer can beselected include, but are not limited to, those disclosed at column 24,line 46 through column 28, line 11 of U.S. Pat. No. 7,465,414 B2, whichdisclosure is incorporated herein by reference.

Further examples of coating compositions from which the optionalprotective layer can be prepared, with some embodiments, include but arenot limited to: (meth)acrylate based protective coating compositions,such as described in U.S. Pat. No. 7,410,691; radiation curable acrylatebased protective coating compositions, such as described in U.S. Pat.No. 7,452,611 B2; thermally cured protective coating compositions, suchas described in U.S. Pat. No. 7,261,843; maleimide based protectivecoating compositions, such as described in U.S. Pat. No. 7,811,480; anddendritic polyester (meth)acrylate based protective coatingcompositions, such as described in U.S. Pat. No. 7,189,456.

The optional anti-reflective layer can be selected from art-recognizedanti-reflective layers (or coatings), and typically includes at leasttwo layers each having a different refractive index. With someembodiments, the optional anti-reflective layer includes a first layerhaving a refractive index of from 1.6 to 2.5, or from 1.95 to 2.4, and asecond layer having a refractive index of from 1.30 to 1.48, or from1.38 to 1.48. The optional anti-reflective layer includes, with someembodiments, a plurality of such alternating first and second layers.With some embodiments, the first layer of the optional anti-reflectivelayer includes at least one of, TiO₂, Ti₂O₃, Ti₃O₅, Pr₆O₁₁+xTiO₂, CeO₂,HfO₂, Ta₂O₅, ZrO₂, and SnO₂. With some embodiments, the second layer ofthe optional anti-reflective layer includes at least one of, SiO₂, MgF₂,AlF₃, BaF₂, Na₅Al₃F₁₄, Na₃AlF₆, and YF₃. Examples of anti-reflectivelayers from which the optional anti-reflective layer can be selected aredescribed in U.S. Pat. No. 6,175,450 B1 at column 1, line 56 throughcolumn 2, line 7; column 2, lines 50-65; and column 5, lines 22-58,which disclosure is incorporated herein by reference.

Each optional polarizing layer can, with some embodiments, be selectedfrom art-recognized polarizing layers. With some embodiments, eachoptional polarizing layer is a conventional linearly polarizing layerformed from one or more layers of unilaterally stretched polymer films,such as unilaterally stretched polyvinyl alcohol films, optionallycontaining a dichroic material.

Each optional reflective layer can be selected from art-recognizedreflective layers. With some embodiments, each optional reflective layeris selected from metal foils, deposited metal layers (such as metallayers deposited by art-recognized sputtering methods), and combinationsthereof. The metal of each optional reflective layer can be selectedfrom art-recognized metals, such as, but not limited to, aluminum,copper, tungsten, tin, zinc, silver, gold, nickel, chromium, andcombinations of two or more thereof.

The optional photochromic layer can include a single layer or multiplelayers, each having the same or a different composition. The optionalphotochromic layer typically includes an organic matrix, such as athermoplastic organic matrix and/or a crosslinked organic matrix, suchas described previously herein with regard to the optional primer layer.Each optional photochromic layer includes one or more art-recognizedphotochromic compounds and/or photochromic-dichroic compounds. Classesof photochromic compounds that can be included in each optionalphotochromic layer include, but are not limited to, indeno-fusednaphthopyrans, naphtho[1,2-b]pyrans, naphtho[2,1-b]pyrans,spirofluoroeno[1,2-b]pyrans, phenanthropyrans, quinolinopyrans,fluoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines,spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines,fulgides, fulgimides, diarylethenes, diarylalkylethenes,diarylalkenylethenes, and combinations of two or more thereof.

The photochromic compounds that can be included in the photochromiclayer of the optical element of the present invention include, or canbe, with some embodiments, photochromic-dichroic materials andcompounds. The photochromic-dichroic materials and compounds can, withsome embodiments, be selected from art-recognized photochromic-dichroicmaterials and compounds. Photochromic-dichroic compounds typically havea photochromic group (P) and at least one lengthening agent or group (L)covalently bonded to the photochromic group. The photochromic groups ofthe photochromic-dichroic compounds can be selected from those classesand examples as described previously herein with regard to thephotochromic compounds, such as, but not limited to, pyrans, oxazines,fulgides, and indeno-fused naphthopyrans. Examples ofphotochromic-dichroic compounds that can be included in the photochromiclayer of the optical elements of the present invention, include, but arenot limited to those disclosed in U.S. Pat. No. 7,256,921 B2 at column19, line 3 through column 22, line 46, which disclosure is incorporatedherein by reference. Examples of lengthening groups (L) and photochromicgroups (P) include, but are not limited to those disclosed in U.S. Pat.No. 7,256,921 B2 at column 22, line 47 through column 35, line 27, whichdisclosure is incorporated herein by reference.

The photochromic compounds and/or photochromic-dichroic compounds can bepresent in the photochromic layer, in amounts (or ratios) such that theresulting photochromic layer (and the coated optical element) exhibitsdesired optical properties. For purposes of non-limiting illustration,the amount and types of photochromic compounds and/orphotochromic-dichroic compounds can be selected such that thephotochromic layer is clear or colorless when the photochromic compoundsand/or photochromic-dichroic compounds are in the closed-form (e.g., inthe bleached or unactivated state), and can exhibit a desired resultantcolor when the photochromic compounds and/or photochromic-dichroiccompounds are in the open-form (e.g., when activated by actinicradiation). The precise amount of the photochromic compounds and/orphotochromic-dichroic compounds that are utilized is not critical,provided that at least a sufficient amount is used to produce thedesired effect. The particular amount of the photochromic compoundsand/or photochromic-dichroic compounds used can depend on a variety offactors, such as but not limited to, the absorption characteristics ofthe photochromic compounds and/or photochromic-dichroic compounds, andthe color and intensity of the color desired upon activation. Inaccordance with some embodiments of the method of the present invention,the amount of the photochromic compound(s) and/or photochromic-dichroiccompound(s) that are present in the photochromic layer formed over theoptical substrate of the optical element can range from 0.01 to 40weight percent, or from 0.05 to 15, or from 0.1 to 5 weight percent,based on the weight of the photochromic coating layer.

With some embodiments, two or more photochromic compounds are used incombination with each other and/or with one or morephotochromic-dichroic compounds, so as to complement one another and toproduce a desired color or hue. For example, mixtures of photochromiccompounds can be used with some embodiments to attain certain activatedcolors, such as a near neutral gray or near neutral brown. See, forexample, U.S. Pat. No. 5,645,767, column 12, line 66 to column 13, line19, the disclosure of which is specifically incorporated by referenceherein, which describes the parameters that define neutral gray andbrown colors.

The photochromic layer can have any suitable thickness, provided itprovides a desirable level of photochromic properties, such as but notlimited to a desirable range of optical density values. With someembodiments, each photochromic layer independently has a thickness offrom 0.5 to 50 microns, such as from 1 to 45 microns, or from 2 to 40microns, or from 5 to 30 microns, or from 10 to 25 microns.

Each optional liquid crystal layer can include a single layer ormultiple layers, each having the same or a different composition. Theoptional liquid crystal layer typically includes an organic matrix, suchas a thermoplastic organic matrix and/or a crosslinked organic matrix,such as described previously herein with regard to the optional primerlayer, but further possessing liquid crystal properties. With someembodiments each optional liquid crystal layer includes a liquid crystalmaterial selected from art-recognized materials, such as, but notlimited to, liquid crystal compounds, liquid crystal oligomers, liquidcrystal polymers, dichroic compounds, photochromic-dichroic compounds,and combinations thereof. The liquid crystal layer can be applied byart-recognized methods, such as described previously herein with regardto the alignment layer.

The optical element, with some embodiments of the present invention,further includes a liquid crystal layer, such as described above, overat least a portion of the alignment layer, where at least a portion ofthe liquid crystal layer is at least partially aligned with an alignmentdirection of the alignment layer. The alignment layer can be providedwith an alignment direction in accordance with art-recognized methods,such as described previously herein.

The present invention is more particularly described in the followingexamples, which are intended as illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLES

In Part 1 of the following examples, there are provided descriptions ofthe preparation of monomers from which polymers of the present inventioncan be prepared (Examples 1-17). In Part 2 of the following examples,there are provided descriptions of the preparation of polymers accordingto the present invention (Examples A-X). In Part 3 of the followingexamples, the preparation of alignment polymer solutions and liquidcrystal coating formulations are described. In Part 4 of the followingexamples, there is described the formation and evaluation of testsamples having in sequence: (i) a solvent cleaned and corona treatedsubstrate; (ii) an at least partially aligned alignment polymer layer on(i); and (iii) a cured liquid crystal coating formulation layer on (ii).

Part 1

Monomers from which the polymers of the present invention can beprepared are described in the following Examples 1-17.

Example 1 Step 1

While stirring under a nitrogen atmosphere, 4-hydroxybenzoic acid (20.8g) and 2-aminophenol (16.4 g) were added to dichlorobenzene (150 mL) ina single neck round bottom flask fitted with a Dean-Stark trap andreflux condenser. Boric acid (1.2 g) was added and the reaction mixturewas refluxed at 205° C. for 22 hours. After cooling to room temperature,the solidified mixture was added to hexanes (600 mL) and stirred for 30minutes. The precipitated solid was collected and dried under vacuum toyield an off-white powder (29.13 g). NMR spectrum of the resultingmaterial was consistent with 4-benzo[d]oxazol-2-yl)phenol.

Step 2

While stirring under a nitrogen atmosphere, the product from Step 1(10.0 g), 6-chlorohexan-1-ol (7.11 g) and potassium carbonate (9.81 g)were combined in dimethylformamide (70 mL). The reaction mixture washeated to 80° C. for 18 hours. After cooling to room temperature, thereaction mixture was poured into ice water. The precipitated solid wascollected and dried under vacuum to yield an off-white powder (14.72 g).NMR spectrum of the resulting material was consistent with6-(4-(benzo[d]oxazol-2-yl)phenoxy)hexan-1-ol.

Step 3

While stirring under a nitrogen atmosphere, the product from Step 2(7.00 g), triethylamine (5.70 g), dimethylaminopyridine (0.035 g) and3,5-di-tert-4-butylhydroxytoluene (0.10 g) were dissolved indichloromethane (100 mL). The reaction mixture was cooled in an ice bathand methacryloyl chloride (3.53 g) was added slowly. After addition wascomplete, the reaction mixture was allowed to warm to room temperatureand stirred for 16 hours. The reaction mixture was washed with saturatedsodium bicarbonate and brine, followed by drying with magnesium sulfate.After removing organic solvent under reduced pressure, the crude residuewas purified by silica gel chromatography and recrystallization fromhexanes/ethyl acetate to yield a colorless solid (5.04 g). NMR spectrumof the resulting material was consistent with6(4-(benzo[d]oxazol-2-yl)phenoxy)hexyl methacrylate.

Example 2

While stirring under a nitrogen atmosphere, the product from Example 1,Step 1 (0.69 g), 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid(1.20 g), dimethylaminopyridine (0.04 g),3,5-di-tert-4-butylhydroxytoluene (0.10 g) andN,N′-dicyclohexylcarbodiimide (0.74 g) were dissolved in dichloromethane(20 ml). After 16 hours, the reaction mixture was filtered to removeurea byproduct and the filtrate was concentrated under reduced pressure.The residue was purified by silica gel chromatography followed byrecrystallization from hexanes/ethyl acetate to yield a colorless solid(1.44 g). NMR spectrum of the resulting material was consistent with4-(benzo[d]oxazol-2-yl)phenyl4-((6-((methacryloyloxy)hexyl)oxy)-3-methoxybenzoate.

Example 3

The procedure of Example 2 was followed, except an equimolar amount of4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in place of4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid. A colorlesssolid (4.05 g) was obtained and NMR spectrum was consistent with4-(benzo[d]oxazol-2-yl)phenyl 4-((6-methacryloyloxy)hexyl)oxy)benzoate.

Example 4

The procedure of Example 2 was followed, except an equimolar amount of3-fluoro-4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in placeof 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid. A colorlesssolid (2.49 g) was obtained and NMR spectrum was consistent with4-(benzo[d]oxazol-2-yl)phenyl3-fluoro-4-((6-methacryloyloxy)hexyl)oxy)benzoate.

Example 5

The procedure of Example 2 was followed, except an equimolar amount of4-((6-(methacryloyloxy)hexyl)oxy)-3-methylbenzoic acid was used in placeof 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid. A colorlesssolid (0.61 g) was obtained and NMR spectrum was consistent with4-(benzo[d]oxazol-2-yl)phenyl4-((6-methacryloyloxy)hexyl)oxy)-3-methylbenzoate.

Example 6 Step 1

Syringic acid (18.7 g) was added to a solution of potassium hydroxide(13.24 g) in ethanol (225 mL)/water (75 mL) and heated to reflux for 1hour. After cooling to room temperature,2-((6-chlorohexyl)oxy)tetrahydro-2H-pyran (25.0 g) and potassium iodide(0.5 g) in ethanol/water mixture (75 mL) were added drop wise and thereaction was refluxed for 72 hours. Ethanol was removed under reducedpressure and the aqueous mixture was neutralized with 1.0 M hydrochloricacid then extracted with dichloromethane. The organic layers werecombined, dried with magnesium sulfate and concentrated under reducedpressure. The residue (37.4 g) was used without further purification.

Step 2

While stirring under a nitrogen atmosphere, the product from Step 1(9.94 g), the product from Example 1, Step 1 (5.00 g),dimethylaminopyridine (0.03 g) and N,N′-dicyclohexylcarbodiimide (5.36g) were dissolved in dichloromethane (120 ml). After 24 hours, thereaction mixture was filtered to remove urea byproduct and the filtratewas concentrated under reduced pressure. The crude residue was purifiedby silica gel chromatography to yield a colorless solid (4.56 g).

Step 3

The product from Step 2 (4.50 g) was dissolved in tetrahydrofuran (40mL) with methanol (40 mL). p-Toluenesulfonic acid monohydrate (0.15 g)was added and the mixture was heated to reflux. After 6 hours, themixture was cooled to room temperature, the volume was decreased underreduced pressure and the concentrate was added to water to precipitatethe product. A colorless solid was collected (3.78 g).

Step 4

The procedure of Example 1, Step 3 was followed, substituting theproduct of Step 3 above (3.70 g) in place of the product of Example 1,Step 2. A colorless solid (2.60 g) was obtained and NMR spectrum wasconsistent with 4-(benzo[d]oxazol-2-yl)phenyl4-((6-methacryloyloxy)hexyl)oxy)-3,5-dim ethyl benzoate.

Example 7 Step 1

Vanillic acid (8.41 g) and 2-aminophenol (5.46 g) were combined in a 100mL round bottom flask. Trimethylsilyl polyphosphate (25 mL) was addedneat and the mixture was heated to 180° C. for 45 minutes. The blackmixture was poured over ice and stirred for 16 hours. The precipitatewas filtered and dried to yield a greenish grey powder (10.63 g). NMRspectrum was consistent with 4-(benzo[d]oxazol-2-yl)-2methoxyphenol.

Steps 2 and 3

The procedure of Example 1, Steps 2 and 3 were followed, except anequimolar amount of the product of Step 1 above was used in place of theproduct of Example 1, Step 2 to yield an off-white solid (2.60 g)intermediate after Step 2. The final product was a colorless solid (1.02g) with an NMR spectrum consistent with6-(4-(benzo[d]oxazol-2-yl)-2-methoxyphenoxy)hexyl methacrylate.

Example 8 Step 1

The procedure of Example 7, Step 1 was followed, except an equimolaramount of syringic acid was used in place of vanillic acid. A purplepowder (10.84 g) was obtained and NMR spectrum was consistent with4-(benzo[d]oxazol-2-yl)-2,6-dimethoxyphenol.

Steps 2 and 3

The procedure of Example 1, Steps 2 and 3 were followed, except anequimolar amount of the product of Step 1 above was used in place of theproduct of Example 1, Step 2 to yield a red oil (2.95 g) after Step 2.The final product after Step 3 was an off-white solid (1.79 g) with anNMR spectrum consistent with6-(4-(benzo[d]oxazol-2-yl)-2,6-dimethoxyphenoxy)hexyl methacrylate.

Example 9 Step 1

Benzo[b]furan-2-ylboronic acid (9.0 g), 4-iodophenol (11.12 g), andsodium carbonate (10.71 g) were added to a mixture of acetone (270 mL)and water (315 mL). The mixture was de-gassed for 15 minutes, palladiumacetate (1.13 g) was added and the reaction stirred at room temperaturefor 5 hours. Acetone was removed under reduced pressure and the aqueouslayer was extracted with ethyl acetate. The organic extracts werecombined, dried with magnesium sulfate, filtered over celite andconcentrated under reduced pressure. The residue was purified by silicagel chromatography followed by recrystallization from hexanes/ethylacetate to yield colorless crystals (8.58 g).

Steps 2 and 3

The procedure of Example 1, Steps 2 and 3 were followed, except anequimolar amount of the product of Step 1 above (2.343 g) was used inplace of the product of Example 1, Step 2 to yield a colorless solid(3.23 g) after Step 2. The final product after Step 3 was a colorlesssolid (2.45 g) with an NMR spectrum consistent with6-(4-(benzofuran-2-yl)phenoxy)hexyl methacrylate.

Example 10

While stirring under a nitrogen atmosphere, the product from Example 9,Step 1 (2.50 g), 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid(4.40 g), dimethylaminopyridine (0.15 g),3,5-di-tert-4-butylhydroxytoluene (0.10 g) andN,N′-dicyclohexylcarbodiimide (2.70 g) were dissolved in dichloromethane(60 ml). After 16 hours, the reaction mixture was filtered to removeurea byproduct and the filtrate was concentrated under reduced pressure.The crude residue was purified by silica gel chromatography followed byrecrystallization from hexanes/dichloromethane to yield a colorlesssolid (4.68 g). NMR spectrum of the resulting material was consistentwith 4-(benzofuran-2-yl)phenyl4-((6-((methacryloyloxy)hexyl)oxy)-3-methoxybenzoate.

Example 11

The procedure of Example 10 was followed, except an equimolar amount of4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in place of4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid. A colorlesssolid (4.03 g) was obtained with an NMR spectrum consistent with4-(benzofuran-2-yl)phenyl 4-((6-methacryloyloxy)hexyl)oxy)benzoate.

Example 12 Step 1

The procedure of Example 9, Step 1 was followed, except an equimolaramount of benzo[b]thiophen-2-ylboronic acid was used in place ofbenzo[b]furan-2-ylboronic acid to yield a colorless solid (8.63 g).

Step 2

The procedure of Example 10 was followed, except an equimolar amount ofthe product of Step 1 was used in place of the product of Example 9,Step 1. A colorless solid (3.96 g) was obtained and NMR spectrum wasconsistent with 4-(benzo[b]thiophen-2-yl)phenyl4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoate.

Example 13

While stirring under a nitrogen atmosphere, the product from Example 12,Step 1 (2.50 g), 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (3.71 g),dimethylaminopyridine (0.13 g), 3,5-di-tert-4-butylhydroxytoluene (0.10g) and N,N′-dicyclohexylcarbodiimide (2.50 g) were dissolved indichloromethane (60 ml). After 16 hours, the reaction mixture wasfiltered to remove urea byproduct and the filtrate was concentratedunder reduced pressure. The crude residue was purified by silica gelchromatography followed by recrystallization fromhexanes/dichloromethane to yield a colorless solid (3.84 g). NMRspectrum of the resulting material was consistent with4-(benzo[b]thiophen-2-yl)phenyl4-((6-((methacryloyloxy)hexyl)oxy)benzoate.

Example 14 Step 1

4-(Trifluoromethyl)phenol (10.0 g) and 2-amino-3-hydroxypyridine (8.15g) were combined in 1.0 N sodium hydroxide (245 mL) and heated to 80° C.After 2 hours, the reaction mixture was neutralized with 1.0 Mhydrochloric acid and precipitate was collected. Recrystallization withmethanol and water yielded a light brown solid (9.80 g).

Steps 2 and 3

The procedure of Example 1, Steps 2 and 3 were followed, except theproduct of Step 1 above (3.00 g) was used in place of the product ofExample 1, Step 2 to yield an off-white solid (3.67 g). The finalproduct after Step 3 was a colorless solid (2.15 g) with an NMR spectrumconsistent with 6-(4-(oxazolo[4,5-b]pyridin-2-yl)phenoxy)hexylmethacrylate.

Example 15 Step 1

While stirring under a nitrogen atmosphere,2-(4-methoxyphenyl)benzo[d]thiazole (5.0 g) was dissolved indichloromethane (50 mL) and cooled in an ice bath. Boron tribromide(10.38 g) was added slowly and the reaction mixture was allowed to warmto room temperature. After 16 hours, the reaction was quenched withwater and 1.0 M hydrochloric acid. The layers were separated and theorganic layer was washed with 1.0 M hydrochloric acid followed by brine.The organic layer was dried with magnesium sulfate, concentrated underreduced pressure and the product was precipitated from tetrahydrofuranwith hexanes to yield a colorless solid (4.60 g).

Steps 2 and 3

The procedure of Example 1, Steps 2 and 3 were followed, except theproduct of Step 1 above (3.00 g) was used in place of the product ofExample 1, Step 2 to yield an off-white solid (2.96 g). The finalproduct after Step 3 was a colorless solid (1.26 g) with an NMR spectrumconsistent with 6-(4-(benzo[d]thiazol-2-yl)phenoxy)hexyl methacrylate.

Example 16 Step 1

While stirring under a nitrogen atmosphere, 2-amino-4-methoxyphenol (3.0g) and 4-fluorobenzaldehyde (4.1 g) were combined in methanol (40 mL)and heated at 45° C. for 16 hours. Methanol was removed under vacuum togive the Schiff base as an orange solid. After dissolving indichloromethane (50 mL), 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ,6.0 g) was added portion wise and the reaction mixture became a darkpurple color as the solution stirred for 30 minutes. Dichloromethane wasremoved under vacuum and the residue was taken up in ethyl acetate,washed with saturated sodium bicarbonate followed by brine and driedwith sodium sulfate. The material was purified by silica gelchromatography to yield a colorless solid (4.64 g).

Step 2

The procedure of Example 15, Step 1 was followed, except the product ofStep 1 above (4.5 g) was used in place of the commercially availablematerial to yield a colorless solid (3.82 g) with an NMR spectrumconsistent with 2-(4-fluorophenyl)benzo[d]oxazol-5-ol.

Steps 3 and 4

The procedure of Example 1, Steps 2 and 3 were followed, except theproduct of Step 2 above (2.80 g) was used in place of the product ofExample 1, Step 2 to yield an off-white solid (3.78 g). The finalproduct after Step 4 was a colorless solid (3.02 g) with an NMR spectrumconsistent with 6-((2-(4-fluorophenyl)benzo[d]oxazol-5-yl)oxy)hexylmethacrylate.

Example 17

The procedure of Example 13 was followed, except the product of Example16, Step 2 (1.0 g) was used in place of the product of Example 12,Step 1. A colorless solid (1.37 g) was obtained having an NMR spectrumthat was consistent with 2-(4-fluorophenyl)benzo[d]oxazol-5-yl4-((6-(methacryloyloxy)hexyl)oxy)benzoate.

Part 2

The preparation of polymers according to the present invention aredescribed in the following Examples A through X.

In the following Examples A through X, all reaction mixtures weresubjected to cooling in a dry ice/acetone bath, followed by degassing byvacuum pump and filling with nitrogen for five cycles prior toconducting the describe polymerization reactions.

In the following Examples A through X, molecular weights were determinedby gel permeation chromatography (GPC) in THF, using polystyrenestandards; and in each case weight average molecular weight (Mw) valuesare reported.

Example A

The monomer of Example 1 (2.00 g) and 2,2′-azobis(2-methylpropionitrile)(0.0087 g) were dissolved in cyclopentanone (5 mL) in a 10 mL Schlenkflask. The reaction mixture was cooled and degassed as described above.After warming to room temperature, the mixture was heated to 60° C. for12 hours. The resulting polymer was precipitated in methanol and driedat 40° C. under vacuum to give a colorless solid (1.89 g) with amolecular weight of 79,400.

Example B

The monomer of Example 1 (2.00 g),2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (0.44 g), and2,2′-azobis(2-methylpropionitrile) (0.0087 g), were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (2.32 g) with a molecular weight of80,700.

The following Formula (B-2) is a representative structure of2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate:

Example C

The product from Example 1, Step 3 (1.00 g),(E)-2-methoxy-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl4-((6-(methacryloyloxy)hexyl)oxy)benzoate (0.06 g), and2,2′-azobis(2-methylpropionitrile) (0.005 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 6.5 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.05 g) with a molecular weight of80,000.

The following Formula (C-2) is a representative structure of(E)-2-methoxy-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl4-((6-(methacryloyloxy)hexyl)oxy)benzoate:

Example D

The product from Example 1, Step 3 (1.00 g), methylmethacrylate (0.013g), and 2,2′-azobis(2-methylpropionitrile) (0.005 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 6.5 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.00 g) with a molecular weight of74,000.

Example E

The product from Example 1, Step 3 (1.00 g), butylmethacrylate (0.02 g),and 2,2′-azobis(2-methylpropionitrile) (0.005 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 6.5 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.95 g) with a molecular weight of79,000.

Example F

The product from Example 2 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0031 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.92 g) with a molecular weight of72,000.

Example G

The product from Example 2, Step 3 (2.00 g),(Z)-2-((((butan-2-ylideneamino)oxy)carbonyl)amino)ethyl methacrylate(1.26 g), and 2,2′-azobis(2-methylpropionitrile) (0.0062 g) weredissolved in cyclopentanone (10 mL) in a 25 mL Schlenk flask. Thereaction mixture was cooled and degassed as described above. Afterwarming to room temperature, the mixture was heated to 62° C. for 12hours. The resulting polymer was precipitated in methanol and dried at40° C. under vacuum to give a colorless solid (2.19 g) with a molecularweight of 74,000.

The following Formula (G-2) is a representative structure of(Z)-2-((((butan-2-ylideneamino)oxy)carbonyl)amino)ethyl methacrylate:

Example H

The product from Example 3 (2.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0066 g) were dissolved incyclopentanone (10 mL) in a 25 mL Schlenk flask. The reaction mixturewas cooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 65° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.80 g) with a molecular weight of67,100.

Example I

The product from Example 4 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.003 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.96 g) with a molecular weight of77,200.

Example J

The product from Example 5 (0.50 g) and2,2′-azobis(2-methylpropionitrile) (0.0016 g) were dissolved incyclopentanone (2.5 mL) in a 5 mL Schlenk flask. After warming to roomtemperature, the mixture was heated to 65° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.44 g with a molecular weight of83,500.

Example K

The product from Example 6, Step 4 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.003 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.99 g) with a molecular weight of73,200.

Example L

The product from Example 7, Step 3 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.004 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.78 g) with a molecular weight of74,000.

Example M

The product from Example 8, Step 3 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.004 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.96 g) with a molecular weight of92,700.

Example N

The product from Example 9, Step 3 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.004 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.97 g) with a molecular weight of90,900.

Example O

The product from Example 10 (2.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0062 g) were dissolved incyclopentanone (10 mL) in a 25 mL Schlenk flask. The reaction mixturewas cooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.78 g) with a molecular weight of78,900.

Example P

The product from Example 11 (2.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0066 g) were dissolved incyclopentanone (10 mL) in a 25 mL Schlenk flask. The reaction mixturewas cooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.80 g) with a molecular weight of76,700.

Example Q

The product from Example 12, Step 2 (2.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0060 g) were dissolved incyclopentanone (10 mL) in a 25 mL Schlenk flask. The reaction mixturewas cooled in a dry ice/acetone bath and degassed by vacuum pumpfollowed by filling with nitrogen. The process was repeated five times.After warming to room temperature, the mixture was heated to 62° C. for12 hours. The resulting polymer was precipitated in methanol and driedat 40° C. under vacuum to give a colorless solid (1.81 g) with amolecular weight of 66,000.

Example R

The product from Example 13 (2.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0064 g) were dissolved incyclopentanone (10 mL) in a 25 mL Schlenk flask. The reaction mixturewas cooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (1.89 g).

Example S

The product from Example 14, Step 3 (1.00 g) and2,2′-azobis(2-methylpropionitrile) (0.0043 g) were dissolved incyclopentanone (5 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.91 g) with a molecular weight of20,800.

Example T

The product from Example 15, Step 3 (0.50 g) and2,2′-azobis(2-methylpropionitrile) (0.0021 g) were dissolved incyclopentanone (2.5 mL) in a 5 mL Schlenk flask. The reaction mixturewas cooled and degassed as described above. After warming to roomtemperature, the mixture was heated to 62° C. for 12 hours. Theresulting polymer was precipitated in methanol and dried at 40° C. undervacuum to give a colorless solid (0.45 g) with a molecular weight of58,200.

Example U

The product from Example 1, Step 3 (1.00 g), the product of Example 15,Step 3 (0.18 g), and 2,2′-azobis(2-methylpropionitrile) (0.0051 g) weredissolved in cyclopentanone (5 mL) in a 10 mL Schlenk flask. Thereaction mixture was cooled and degassed as described above. Afterwarming to room temperature, the mixture was heated to 65° C. for 12hours. The resulting polymer was precipitated in methanol and dried at40° C. under vacuum to give a colorless solid (1.10 g) with a molecularweight of 60,100.

Example V

The product from Example 6, Step 1 (1.00 g), the product of Example 15,Step 3 (0.13 g), and 2,2′-azobis(2-methylpropionitrile) (0.0036 g) weredissolved in cyclopentanone (5 mL) in a 10 mL Schlenk flask. Thereaction mixture was cooled and degassed as described above. Afterwarming to room temperature, the mixture was heated to 62° C. for 12hours. The resulting polymer was precipitated in methanol and dried at40° C. under vacuum to give a colorless solid (1.06 g) with a molecularweight of 93,100.

Example W

The product from Example 16, Step 4 (0.50 g) and2,2′-azobis(2-methylpropionitrile) (0.0021 g) were dissolved incyclopentanone (3 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled in a dry ice/acetone bath and degassed by vacuum pump followed byfilling with nitrogen. The process was repeated five times. Afterwarming to room temperature, the mixture was heated to 62° C. for 4hours. The resulting polymer was precipitated in methanol and dried at40° C. under vacuum to give a colorless solid (0.41 g) with a molecularweight (Mw) of 70,160.

Example X

The product from Example 17 (0.65 g) and2,2′-azobis(2-methylpropionitrile) (0.0021 g) were dissolved incyclopentanone (3 mL) in a 10 mL Schlenk flask. The reaction mixture wascooled in a dry ice/acetone bath and degassed by vacuum pump followed byfilling with nitrogen. The process was repeated five times. Afterwarming to room temperature, the mixture was heated to 62° C. for 4hours. The resulting polymer was precipitated in methanol and dried at40° C. under vacuum to give a colorless solid (0.41 g) with a molecularweight (Mw) of 149,000.

Part 3 Part 3-1: Alignment Polymer Solutions

The alignment polymers of Examples A, C, F, G, and U were each dilutedto an alignment polymer solids content of 6 percent by weight, based ontotal solution weight, with cyclopentanone. Each alignment polymersolution was passed through a 30 mm TEFLON syringe filter (having a poresize of 0.45 microns) prior to use in Part 4.

Part 3-2: Liquid Crystal Coating Formulations (LCCF's)

Liquid crystal coating formulations 1, 2, and 3 were prepared using thematerials and amounts (shown in grams) as summarized in the followingTable 1.

TABLE 1 LCCF-1 LCCF-2 LCCF-3 Anisole 3.2 3.2 3.2 BYK ®-322¹ 0.00340.0034 0.0034 RM 257² 2.4 2.4 2.4 RM 105³ 2.4 2.4 2.4 4-methoxyphenol0.0048 0.0048 0.0048 IRGACURE ® 819⁴ 0.0720 0.0720 0.0720 Fixed tintdichroic dye⁵ — 0.105 — Photochromic dichroic dye⁶ — — 0.312 ¹BYK ®-322is an aralkyl modified poly-methyl-alkyl-siloxane commercially availablefrom BYK Chemie, USA. ²RM 257 is a liquid crystal monomer reported to be4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester,commercially available from EMD Chemicals, Inc. ³RM 105 is a liquidcrystal monomer reported to be 4-methoxy-3-methylphenyl4-(6-(acryloyloxy)hexyloxy)benzoate, commercially available from EMDChemicals, Inc. ⁴IRGACURE ® 819 is a photoinitiator commerciallyavailable from BASF Corporation. ⁵The fixed tint dichroic dye is adichroic polyazo dye that was prepared according to Example 1C in thefollowing reference: Shigeo YASUI, Masaru MATSUOKA, Teijiro KITAO,Journal of the Japan Society of Colour Material, Vol. 61 (1988) No. 12p. 678-68. ⁶The photochromic dichroic dye was prepared according toExample 44 of U.S. Pat. No. 8,518,546 B2.

Liquid crystal coating formulations 1 through 3 were prepared bycombining the components and amounts as summarized in Table 1, stirringfor two hours at 80° C., followed by cooling to room temperature. Toeach formulation anhydrous magnesium sulfate was added at 10% by weightof solution, followed by stirring at room temperature for 30 minutes,and then filtering with an EMD Millipore Ultrafree™-CL CentrifugalFilter Device.

Part 4 Part 4-1: Test Substrate Preparation.

Square substrates measuring 5.08 cm by 5.08 cm by 0.318 cm (2 inches(in.) by 2 in. by 0.125 in.) prepared from CR-39® monomer were obtainedfrom Homalite, Inc. Each substrate was cleaned by wiping with a tissuesoaked with acetone and drying with a stream of air.

Each of the acetone cleaned square substrates was corona treated bypassing on a conveyor belt in a Tantec EST Systems Serial No. 020270Power Generator HV 2000 series corona treatment apparatus, equipped witha high voltage transformer. The acetone cleaned square substrates wereexposed to corona generated by 70.00 KV, 1000 Watts while traveling on aconveyor at a belt speed 3 ft/min, which resulted in the formation ofthe test substrates used in Parts 4-2 and 4-3 further herein.

Part 4-2: Application of Alignment Polymer Solutions.

The alignment polymer solutions of Examples A, C, F, G and U prepared inPart 3-1 were each separately applied to separate test substrates(formed in Part 4-1) by spin-coating on the corona treated surface ofthe test substrate by dispensing approximately 1.0 mL of the solutionand spinning the test substrate at 800 revolutions per minute (rpm) for3 seconds, followed by 1,000 rpm for 7 seconds, followed by 2,500 rpmfor 4 seconds using a spin processor from Laurell Technologies Corp.(WS-400B-6NPP/LITE). The test substrates with alignment polymersolutions applied thereto were placed in an oven maintained at 120° C.for 30 minutes, followed by cooling to room temperature.

The dried alignment polymer layer on each of the test substrates was atleast partially ordered by exposure to linearly polarized ultravioletradiation using a 500 W flood exposure source with digital exposurecontroller equipped with a Hg arc lamp (all from Newport Corporation,model no longer commercially available) with a Moxtek wire gridpolarizer (200 mm diameter ProFlux polarizer, PPL04A). The light sourcewas oriented such that the radiation was linearly polarized in a planeperpendicular to the surface of the test substrate. The amount ofultraviolet radiation that each alignment polymer layer was exposed tois summarized as follows: UVA 0.17 W/cm² and 29.9 J/cm²; UVB 0.0 W/cm²and 0.0 J/cm²; UVC 0 W/cm² and 0 J/cm²; and UVV 0.005 W/cm² and 9.466J/cm² in each case as measured using a UV Power Puck™ High energyradiometer from EIT Inc (Serial No. 2066). After at least partiallyordering each alignment polymer layer, the test substrates were cooledto room temperature and kept covered.

Part 4-3: Application of Liquid Crystal Coating Formulations.

The liquid crystal coating formulations (LCCF's 1, 2, and 3) prepared inPart 3-2 were each spin coated at a rate of 1,000 rpm/10 seconds ontothe at least partially ordered alignment polymer layers of the testsquares prepared in Part 4-2. Each LCCF coated test substrate was placedin an oven at 50° C. for 30 minutes. Afterwards, each dried LCCF coatedtest substrate was cured under two ultraviolet lamps in a UV Curing OvenMachine designed and built by Belcan Engineering in nitrogen atmospherewhile running on a conveyor belt at 2 ft/min speed at peak intensitiesof 0.513 Watts/cm² of UVA and 0.236 Watts/cm² of UVV and UV dosages of8.659 Joules/cm² of UVA and 3.887 Joules/cm² of UVV. Curing of the LCCFlayers resulted in the formation of test samples each having insequence: (i) a solvent cleaned and corona treated substrate, asdescribed in Part 4-1; (ii) an at least partially aligned alignmentpolymer layer on (i), as described in Part 4-2; and (iii) a cured LCCFlayer on (ii), as described in Part 4-3.

Test samples coated with LCCF-1 and LCCF-2 were held parallel to thelight source of a Polariscope and turned 90° for determination ofalignment. Test samples coated with LCCF-3 were activated with ambientoutdoor light before evaluation under a Polariscope to confirm alignmentas described above. Alignment was confirmed when a visual difference intransmittance was observed on rotating the test sample. The results ofthe alignment evaluations are summarized in the following Table 2.

TABLE 2 Liquid Crystal Alignment Example Alignment Coating Observed?Number Polymer Formulation (Yes/No) A-1 Example A LCCF-1 Yes C-1 ExampleC LCCF-1 Yes F-1 Example F LCCF-1 Yes G-1 Example G LCCF-1 Yes U-1Example U LCCF-1 Yes A-2 Example A LCCF-2 Yes C-2 Example C LCCF-2 YesF-2 Example F LCCF-2 Yes G-2 Example G LCCF-2 Yes U-2 Example U LCCF-2Yes A-3 Example A LCCF-3 Yes C-3 Example C LCCF-3 Yes F-3 Example FLCCF-3 Yes G-3 Example G LCCF-3 Yes U-3 Example U LCCF-3 Yes

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as to the extent that they are included in theaccompanying claims.

What is claimed is:
 1. A polymer comprising at least one residue of at least one monomer represented by the following Formula (I),

wherein for Formula (I), Ring-A is selected from the group consisting of aryl and heteroaryl, E is N or C—R¹, D is selected from the group consisting of O, S, and N—R², wherein R¹ of E and R² of D are each independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, interrupted hydrocarbyl, and substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected from the group consisting of hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are each independently 0 to 2, provided that the sum of w and e is 2, and each R₈′ is independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof, L¹ and L⁴ are each independently selected from at least one of: a single bond; —O—; —S—; —C(O)—; —S(O)—; —SO₂—; —N═N—; —N(R₁₁′)— where R₁₁′ is selected from the group consisting of hydrogen, hydrocarbyl or substituted hydrocarbyl; —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are each independently 0 to 2, provided that the sum of w and e is 2, and each R₈′ is independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl; hydrocarbyl; substituted hydrocarbyl; interrupted hydrocarbyl; and substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected from the group consisting of hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR₈′)_(w)(R₈′)_(e)—, where w and e are each independently 0 to 2, provided that the sum of w and e is 2, and each R₈′ is independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof, t is 0 to 4, s is, independently for each g, from 1 to 4, g is 0 to 6, provided that the sum of t and g is at least 1, m is, independently for each t, from 0 to 4, q is, independently for each s, from 0 to 4, L² independently for each m, and L⁵ independently for each q, are in each case independently selected from the group consisting of divalent linear or branched C₁-C₂₅ alkyl, divalent interrupted linear or branched C₁-C₂₅ alkyl, divalent linear or branched C₁-C₂₅ perhaloalkyl, divalent interrupted linear or branched C₁-C₂₅ perhaloalkyl, divalent linear or branched C₂-C₂₅ alkenyl, and divalent interrupted linear or branched C₂-C₂₅ alkenyl, wherein each divalent interrupted linear or branched C₁-C₂₅ alkyl, each divalent interrupted linear or branched C₁-C₂₅ perhaloalkyl, and each divalent interrupted linear or branched C₂-C₂₅ alkenyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof, p is, independently for each t, from 0 to 4, provided the sum of m and p is at least 1 for each t that is greater than zero, r is, independently for each s, from 0 to 4, provided the sum of q and r is at least 1 for each s, L³ independently for each p, and L⁶ independently for each r, are in each case independently represented by the following Formula (II-1),

Y is, independently for each p and independently for each r, a divalent linking group selected from the group consisting of a single bond, —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, —N(R⁹)—C(O)—O—, —C(O)—N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, v and u are each independently, for each p and each r, 0 to 5, provided that the sum of v and u is at least 1 for each p that is greater than zero and each r that is greater than zero, Z is, independently for each v, a divalent linking group selected from the group consisting of a single bond, —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, —N(R⁹)—C(O)—O—, —C(O)—N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, the divalent rings,

are each independently selected, for each v and each u, from the group consisting of divalent aryl, substituted divalent aryl, divalent heteroaryl, substituted divalent heteroaryl, divalent cycloalkyl, substituted divalent cycloalkyl, divalent heterocycloalkyl, and substituted divalent heterocycloalkyl, and E¹ and E² are each independently selected from the group consisting of hydrogen, hydrocarbyl, interrupted hydrocarbyl, substituted hydrocarbyl, and substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof, provided that at least one of E¹ and E² independently is, or is independently substituted with, at least one reactive group selected from the group consisting of (linear or branched C₁-C₈ alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, amine, isocyanate, aldehyde, and combinations thereof, provided that a direct L¹-L² link between L¹ and L² is free of two heteroatoms linked together, a direct L¹-L³ link between L¹ and L³ is free of two heteroatoms linked together, and each direct L²-L³ link between each directly linked L² and L³ is free of two heteroatoms linked together, and further provided that a direct L⁴-L⁵ link between L⁴ and L⁵ is free of two heteroatoms linked together, a direct L⁴-L⁶ link between L⁴ and L⁶ is free of two heteroatoms linked together, and each direct L⁵-L⁶ link between each directly linked L⁵ and L⁶ is free of two heteroatoms linked together.
 2. The polymer of claim 1, wherein for Formula (I), Ring-A is aryl, R¹ of E and R² of D are each independently selected from the group consisting of hydrogen, linear or branched C₁-C₂₅ alkyl, linear or branched C₂-C₂₅ alkenyl, C₃-C₁₂ cycloalkyl, C₃-C₁₂ heterocycloalkyl, aryl, and heteroaryl, m is at least 1 for at least one t, q is at least 1 for at least one s, L² is, independently for each m, and L⁵ is, independently for each q, in each case independently selected from the group consisting of divalent linear or branched C₁-C₂₅ alkyl, divalent interrupted linear or branched C₁-C₂₅ alkyl, divalent linear or branched C₁-C₂₅ perhaloalkyl and divalent interrupted linear or branched C₁-C₂₅ perhaloalkyl, wherein each divalent interrupted linear or branched C₁-C₂₅ alkyl and each divalent interrupted linear or branched C₁-C₂₅ perhaloalkyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —C(O)O—, and —OC(O)O—, p is at least 1 for at least one t, r is at least 1 for at least one s, L³ independently for each p, and L⁶ independently for each r, are in each case independently represented by the following Formula (II-2),

wherein the divalent rings,

are each independently selected, for each v and each u, from the group consisting of phenylen-1,4-diyl, substituted phenylen-1,4-diyl, cyclohexan-1,4-diyl, substituted cyclohexan-1,4-diyl, pyrimidin-2,5-diyl, substituted pyrimidin-2,5-diyl, pyridine-2,5-diyl, substituted pyridine-2,5-diyl, naphthalene-2,6-diyl, substituted naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl in which the aromatic ring is substituted, decahydronaphthalene-2,6-diyl, indane-2,5(6)-diyl, fluorene-2,-7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, (1,3,4)thiadiazol-2,5-diyl, (1,3)thiazol-2,5-diyl, (1,3)thiazol-2,4-diyl, thiophen-2,4-diyl, thiophen-2,5-diyl, (1,3)dioxan-2,5-diyl, piperidin-1,4-diyl, and, piperazin-1,4-diyl, and E¹ and E² are each independently selected from the group consisting of hydrogen, linear or branched C₁-C₂₅ alkyl, interrupted linear or branched C₁-C₂₅ alkyl, linear or branched C₂-C₂₅ alkenyl, and interrupted linear or branched C₂-C₂₅ alkenyl, wherein each interrupted linear or branched C₁-C₂₅ alkyl and each interrupted linear or branched C₂-C₂₅ alkenyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, and —C(O)O—, provided that at least one of E¹ and E² independently is, or is independently substituted with, at least one reactive group selected from the group consisting of (meth)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, and combinations thereof.
 3. The polymer of claim 2, wherein for Formula (I), Ring-A is phenyl, R¹ of E and R² of D are each independently selected from the group consisting of hydrogen and linear or branched C₁-C₁₀ alkyl, L² is, independently for each m, and L⁵ is, independently for each q, in each case independently selected from the group consisting of divalent linear or branched C₁-C₁₀ alkyl, divalent interrupted linear or branched C₁-C₁₀ alkyl, divalent linear or branched C₁-C₁₀ perfluoroalkyl, and divalent interrupted linear or branched C₁-C₁₀ perfluoroalkyl, wherein each divalent interrupted linear or branched C₁-C₁₀ alkyl and each divalent interrupted linear or branched C₁-C₁₀ perfluoroalkyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —C(O)O—, and —OC(O)O—, independently for each L³, and independently for each L⁶, Z is, independently for each v, selected from the group consisting of a single bond, —O— and —C(O)O—, and the divalent rings,

are each independently selected, for each v and each u, from the group consisting of phenylen-1,4-diyl, substituted phenylen-1,4-diyl, cyclohexan-1,4-diyl, and substituted cyclohexan-1,4-diyl, and E¹ and E² are each independently selected from the group consisting of hydrogen, linear or branched C₁-C₁₀ alkyl, and interrupted linear or branched C₁-C₁₀ alkyl, wherein each interrupted linear or branched C₁-C₁₀ alkyl is independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, and —C(O)O—, provided that at least one of E¹ and E² independently is, or is independently substituted with, at least one reactive group selected from the group consisting of (meth)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, and combinations thereof.
 4. The polymer of claim 3, wherein for Formula (I), E¹ and E² are each independently selected from the group consisting of hydrogen, linear or branched C₁-C₁₀ alkyl, and interrupted linear or branched C₁-C₁₀ alkyl, wherein each interrupted linear or branched C₁-C₁₀ alkyl is independently interrupted with at least one interrupting group selected from the group consisting of —O— and —C(O)O—, provided that at least one of E¹ and E² independently is, or is independently substituted with, (meth)acryloyl.
 5. The polymer of claim 4, wherein said polymer further comprises at least one residue of an additional monomer selected from the group consisting of (meth)acrylic acid, hydrocarbyl (meth)acrylate, substituted hydrocarbyl (meth)acrylate, unsubstituted styrene, substituted styrene, and combinations thereof.
 6. The polymer of claim 3, wherein for Formula (I), D is O.
 7. The polymer of claim 1, wherein for Formula (I), L¹ and L⁴ are each independently selected from the group consisting of one of the following Formulas IIIa, IIIb, IIIc, IIId, IIIe, or IIIf,

wherein R⁷ is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl,

wherein R⁸ is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl,

wherein R^(b) is selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and

wherein R^(c) and R^(d) are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl.
 8. The polymer of claim 7, wherein R⁷ and R⁸ for each of L¹ and L⁴ are each independently selected from the group consisting of divalent linear or branched C₁-C₂₅ alkyl, divalent linear or branched C₂-C₂₅ alkenyl, divalent C₃-C₁₂ cycloalkyl, divalent C₃-C₁₂ heterocycloalkyl, divalent aryl, and divalent heteroaryl.
 9. The polymer of claim 8, wherein for Formula (I), L¹ and L⁴ are each independently the divalent linking group represented by Formula IIId, wherein each R⁸ is independently divalent linear or branched C₁-C₈ alkyl.
 10. The polymer of claim 1, wherein for Formula (I), at least one of, divalent Ring-(B) and divalent Ring-(C), are each independently selected from the group consisting of divalent aryl, substituted divalent aryl, divalent heteroaryl, and substituted divalent heteroaryl.
 11. The polymer of claim 2, wherein for Formula (I), at least one of, divalent Ring-(B) and divalent Ring-(C), are each independently selected from the group consisting of phenylen-1,4-diyl, substituted phenylen-1,4-diyl, pyrimidin-2,5-diyl, substituted pyrimidin-2,5-diyl, pyridine-2,5-diyl, substituted pyridine-2,5-diyl, naphthalene-2,6-diyl, substituted naphthalene-2,6-diyl, and phenanthrene-2,7-diyl.
 12. The polymer of claim 3, wherein for Formula (I), each L³ and each L⁶, are in each case independently selected from the group consisting of the following formulas,


13. The polymer of claim 1, wherein for Formula (I), at least one of L³ and L⁶ independently is a mesogenic group, and said polymer is a mesogenic polymer.
 14. The polymer of claim 1, further comprising at least one residue of at least one further monomer represented by the following Formula (V), E³(L³)_(p)-(L²)_(m)_(t′)L¹-E⁴  Formula (V) wherein, t′ is from 1 to 4, L¹, L², and L³, are each independently as described for Formula (I), m is, independently for each t′, from 0 to 4, p is, independently for each t′, from 0 to 4, provided the sum of m and p is at least one for each t′, and E³ and E⁴ are each independently selected from the group consisting of hydrogen, hydrocarbyl, interrupted hydrocarbyl, substituted hydrocarbyl, and substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO₂—, —N(R⁹)—, and —Si(R⁹)(R¹⁰)— wherein R⁹ and R¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof, provided that E³ is, or is substituted with, at least one reactive group selected from the group consisting of (linear or branched C₁-C₈ alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, amine, isocyanate, aldehyde, and combinations thereof.
 15. The polymer of claim 14, wherein said polymer comprises at least one polymer segment represented by the following Formula (VI),

wherein E^(1a) independently for each x is a divalent residue of E¹ of Formula (I), E^(2a) independently for each y is a divalent residue of E² of Formula (I), and E^(3a) independently for each z is a divalent residue of E³ of Formula (V), h is from 1 to 10,000, x is from 0 to 10 for each h, y is from 0 to 10 for each h, and z is from 0 to 10 for each h, provided that the sum of x, y, and z is at least one for each h, and provided that the sum of x and y is at least one for at least one h.
 16. An alignment layer comprising at least one polymer of claim
 1. 17. An article of manufacture comprising said alignment layer of claim
 16. 18. The article of manufacture of claim 17, wherein said article of manufacture is an optical element comprising: an optical substrate; and said alignment layer resides over at least a portion of a surface of said substrate.
 19. The optical element of claim 18, wherein said alignment layer is at least partially aligned by exposing at least a portion of said alignment layer to at least one of, a magnetic field, an electric field, linearly polarized radiation, and shear force.
 20. The optical element of claim 18, wherein said optical element is selected from an ophthalmic element, a display element, a window, a mirror, and a liquid crystal cell element.
 21. The ophthalmic element of claim 20, wherein said ophthalmic element is selected from a corrective lens, a non-corrective lens, a contact lens, an intra-ocular lens, a magnifying lens, a protective lens, and a visor.
 22. The optical element of claim 18, further comprising, over at least a portion of said surface of said substrate, at least one additional layer, wherein each additional layer is independently selected from a primer layer, a protective layer, an anti-reflective layer, a reflective layer, a polarizing layer, a photochromic layer, a liquid crystal layer, and combinations thereof.
 23. The optical element of claim 18, further comprising a liquid crystal layer over at least a portion of said alignment layer, wherein at least a portion of said liquid crystal layer is at least partially aligned with an alignment direction of said alignment layer. 